CN100591708C - High-molecular copolymer containing metal coordination compound and organic electroluminescence element using the same - Google Patents
High-molecular copolymer containing metal coordination compound and organic electroluminescence element using the same Download PDFInfo
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- CN100591708C CN100591708C CN200480016774A CN200480016774A CN100591708C CN 100591708 C CN100591708 C CN 100591708C CN 200480016774 A CN200480016774 A CN 200480016774A CN 200480016774 A CN200480016774 A CN 200480016774A CN 100591708 C CN100591708 C CN 100591708C
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 134
- 229920001577 copolymer Polymers 0.000 title claims abstract description 129
- 229910052751 metal Inorganic materials 0.000 title abstract description 112
- 239000002184 metal Substances 0.000 title abstract description 112
- 238000005401 electroluminescence Methods 0.000 title description 4
- 239000000178 monomer Substances 0.000 claims abstract description 91
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 71
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- 150000004696 coordination complex Chemical class 0.000 claims description 99
- 125000004432 carbon atom Chemical group C* 0.000 claims description 84
- 125000000217 alkyl group Chemical group 0.000 claims description 74
- 125000003118 aryl group Chemical group 0.000 claims description 65
- 230000014509 gene expression Effects 0.000 claims description 64
- 125000001072 heteroaryl group Chemical group 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 62
- 150000004646 arylidenes Chemical group 0.000 claims description 59
- 229910052799 carbon Inorganic materials 0.000 claims description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 35
- 125000005843 halogen group Chemical group 0.000 claims description 34
- 229910052741 iridium Inorganic materials 0.000 claims description 31
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 31
- 238000006467 substitution reaction Methods 0.000 claims description 27
- 125000001118 alkylidene group Chemical group 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 8
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052763 palladium Inorganic materials 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010948 rhodium Chemical group 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Chemical group 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical group [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 14
- 150000001721 carbon Chemical group 0.000 claims 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 3
- 125000003453 indazolyl group Chemical class N1N=C(C2=C1C=CC=C2)* 0.000 claims 1
- 125000000732 arylene group Chemical group 0.000 abstract description 10
- 125000005549 heteroarylene group Chemical group 0.000 abstract description 2
- 239000003086 colorant Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 238
- 239000007787 solid Substances 0.000 description 144
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 135
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 134
- -1 polyparaphenylene-vinylene Polymers 0.000 description 112
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 94
- 239000002585 base Substances 0.000 description 78
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 52
- 238000003756 stirring Methods 0.000 description 49
- 239000000463 material Substances 0.000 description 46
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 44
- 238000001556 precipitation Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 39
- 238000000967 suction filtration Methods 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000011575 calcium Substances 0.000 description 28
- 239000000284 extract Substances 0.000 description 26
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 26
- 239000003456 ion exchange resin Substances 0.000 description 24
- 229920003303 ion-exchange polymer Polymers 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 22
- 239000007818 Grignard reagent Substances 0.000 description 21
- 150000004795 grignard reagents Chemical class 0.000 description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 20
- 230000002194 synthesizing effect Effects 0.000 description 20
- 125000006617 triphenylamine group Chemical group 0.000 description 19
- 239000011521 glass Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 16
- 235000015320 potassium carbonate Nutrition 0.000 description 16
- 239000003513 alkali Substances 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 12
- 239000003957 anion exchange resin Substances 0.000 description 12
- 239000004327 boric acid Substances 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 12
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 125000000950 dibromo group Chemical group Br* 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 10
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
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- ATPAWRVOKDYOLR-UHFFFAOYSA-N benzene oxadiazole Chemical class C1=CC=CC=C1.O1N=NC=C1 ATPAWRVOKDYOLR-UHFFFAOYSA-N 0.000 description 6
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- 238000000576 coating method Methods 0.000 description 5
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
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- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 125000005553 heteroaryloxy group Chemical group 0.000 description 4
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
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- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 4
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 150000004059 quinone derivatives Chemical class 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- ZRIUSVITVGWLSQ-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 ZRIUSVITVGWLSQ-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
A high-molecular copolymer containing a metal coordination compound capable of blue phosphorescence of high color purity. There is further provided a high-molecular copolymer containing a metal coordination compound of prolonged driving life capable of emitting lights of various colors ranging from blue to red. In particular, there is provided a high-molecular copolymer containing a metal coordination compound, characterized by comprising any of metal coordination compound monomer units represented by the formulae (1) to (12): B: >O, >S, >C=O, >SO2, >CR2 together with at least one monomer unitselected from the group consisting of a substituted or unsubstituted quinoline monomer unit, a substituted or unsubstituted arylene and/or heteroarylene monomer unit, a substituted or unsubstituted branched structure monomer unit and a substituted or unsubstituted conjugated monomer unit.
Description
Technical field
The present invention relates to a kind of organic electroluminescent (EL) element that contains the high-molecular copolymer of new metal complex and use it.
Background technology
Electroluminescent cell has been subjected to attracting attention on big area solid-state (solid state) light source purposes as for example substitute of incandescent light, gas filling lamp etc.On the other hand, (flat panel display, PFD) the strongest self-emitting display (display) of the liquid-crystal display in the field also has been subjected to attracting attention as replacing flat-panel screens.Particularly, element material is by organic electroluminescent (EL) element that organic materials constituted, and just strides forward towards commercialization as full-color (full color) FPD of low power consumption type.Wherein, utilize macromolecular material to constitute the organic EL of the polymer of organic materials, its with must in vacuum system, compare by the organic EL of film forming low molecule-type, because can print, ink-jet simple and easy film forming such as (ink-jet) etc., therefore for big picture OLED display from now on, be a kind of indispensable element.
Up to now, in the polymer organic EL, used conjugation (conjugation) polymkeric substance (polymer) for example polyparaphenylene-vinylene (p-phenylene-vinylene) (for example with reference to international disclose the 90/13148th trumpeter's volume) and non-conjugated polymeric thing (with reference to I.Sokolik etc., Applied Physics periodical (J.Appl.Phys.1993.74,3584)) any polymer materials in.Yet the luminescent lifetime of this element is shorter, becomes the obstacle in the field of construction full-color display.
Though proposed the polymer organic EL that uses various poly-fluorenes (polyfluorene) types and gather the conjugated polymers of right-penylene (p-phenylene) type in recent years for addressing the above problem, but aspect stable, do not find the product that can meet the demands.
As a method that addresses this problem, proposed to be used to the element of the phosphorescence of self-excitation triplet state.If can be used to the phosphorescence of self-excitation triplet state, then compare and to expect to obtain at least 3 times luminous quantum efficiency on the principle with the situation of the fluorescence that is used to the self-excitation singlet state.In addition, if also consider utilization simultaneously, then can expect to obtain 4 times, i.e. 100% luminous quantum efficiency on the principle by the exciton that produces from reporting to the leadship after accomplishing a task between the item of the high singlet state of energy when triplet state changes.
As research example up to now, for example .Appl.Phys.Lett.1999.75.4 such as M.A.Baldo etc. is arranged.In the document, used material shown below.The abbreviation of each material is as follows.
Alq
3: aluminium-hydroxyquinoline complex compound (tris (8-quinolinolato) aluminum)
α-NPD:N, N '-dinaphthyl-1-base-N, N '-phenylbenzene-biphenyl-4,4 '-diamines (N, N '-Di-naphthalen-1-yl-N, N '-diphenyl-biphenyl-4,4 '-diamine)
CBP:4,4 '-N, N '-two carbazoles-biphenyl (4,4 '-N, N '-dicarbazole-biphenyl)
BCP:2, and 9-dimethyl-bathophenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)
Ir (ppy)
3: iridium-phenylpyridine complex compound (tris (2-phenylpyridine) iridium)
In addition, as the luminous example that is used to from triplet state, open the spy that flat 11-329739 communique, spy are opened flat 11-256148 communique, the spy opens in flat 8-319482 communique etc. on the books.
Summary of the invention
In view of the above-mentioned problems, purpose of the present invention is providing a kind of high-molecular copolymer that contains metal complex, and it can send blue to redness and the good phosphorescence of purity of color.And another object of the present invention is providing a kind of high-molecular copolymer that contains metal complex, and it can send blue each extremely red coloured light and have the long driving life-span.
In addition, purpose of the present invention is providing a kind of polymer composition, and it can send blue to redness and the good phosphorescence of purity of color.And another object of the present invention is providing a kind of polymer composition, and it can send blue each extremely red coloured light and have the long driving life-span.
In addition, purpose of the present invention is providing a kind of organic electroluminescent device, and it can send blue each extremely red coloured light and have good luminescent characteristic and reliability.
The present invention contains the polymer copolymerization that has imported substituent metal complex miscellaneous as dentate through conscientiously discovering, be from blueness to red all can be luminous, drive long excellent material of life-span.
That is to say, in the present invention, a kind of high-molecular copolymer that contains metal complex is provided, its comprise with arbitrary metal complex monomeric unit of formula (1)～(12) expressions be selected from replace or the conjugative monomer unit of the branched structure monomeric unit of the arylidene (arylene) of quinoline (quinoline) monomeric unit, replacement or the non-replacement of non-replacement and/or heteroarylidene monomeric unit, replacement or non-replacement and replacement or non-replacement in one or more monomeric unit.
B：＞O，＞S，＞C＝O，＞SO
2，＞CR
2
(in the formula, M is iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os), palladium (Pd) or platinum (Pt); N is 1 or 2; Ring A is the ring compound that contains with M bonded nitrogen-atoms; X
1～X
7And R represents respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8,-NR
9R
10Substituting group, R wherein
1～R
10Represent hydrogen atom separately respectively, halogen atom, cyano group (cyano), nitro, carbon number is 1～22 a straight chain, part or all of hydrogen atom on ring-type or branched-chain alkyl or these bases replaced by halogen atom and halogen-substituted alkyl, carbon number is 6～30 a aryl (aryl), carbon number is that 2～30 heteroaryl or the carbon number aralkyl (aralkyl) that is 7～30 or part or all of the hydrogen atom on these bases are replaced the halogen substituted aryl that gets by halogen atom, the halogen substituted heteroaryl, the halogen substituted aralkyl; R
1～R
10Can be separately identical, also can be difference, X
1～X
7Can be separately identical, also can be difference; Ring A can have and use X
1-X
7The identical substituting group of group of definition; Ring C be with the M bonded, with in conjunction with the basic compound that combines; Ring C can have and use X
1-X
7The identical substituting group of group of definition).
In addition, preferably contain in the high-molecular copolymer of metal complex, contain above-mentioned formula (1)～(12) represented any metal complex monomeric unit, replacement or non-replacement with suc as formula quinoline (quinoline) monomeric unit shown in (13-1), with the arylidene (arylene) and/or heteroarylidene (hetero arylene) monomeric unit of replacement or non-replacement
Perhaps
(in the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, wherein, R
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl), that these substituting groups can be separately is identical, also can be difference, but is the substituting group that is incorporated into the position of substitution in the quinoline residue; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene (Arylene); E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-)
m-O-(m is 1～3 integer) combines base with the divalent of-Q-, wherein W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, Ra is an alkylidene group, Ar ' is an arylidene, Ra ' represents to be selected from the base of alkylidene group, arylidene and alkylidene group/arylidene mixed base separately respectively, Het ' is a heteroarylidene, and Q is the divalent base that contains level Four carbon), wherein, in conjunction with the group of above-mentioned each monomeric unit, have structure with formula (14) expression:
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In addition, preferably contain in the high-molecular copolymer of metal complex, contain above-mentioned formula (1)～(12) represented any metal complex monomeric unit, replacement or non-replacement with suc as formula quinoline (quinoline) monomeric unit shown in (13-1) and the branched structure monomeric unit of replacement or non-replacement
(in the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but is the substituting group that is incorporated into the position of substitution in the quinoline residue; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene (Arylene); E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-)
m-O-(m is 1～3 integer) combines base with the divalent of-Q-, wherein W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, Ar ' is an arylidene, Ra ' represents to be selected from the base of alkylidene group, arylidene and alkylidene group/arylidene mixed base separately respectively, Het ' is a heteroarylidene, and Q is the divalent base that contains level Four carbon), wherein, in conjunction with the base of above-mentioned each monomeric unit, have structure with formula (14) expression:
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In addition, preferably contain in the high-molecular copolymer of metal complex, contain any represented metal complex monomeric unit of above-mentioned formula (1)～(12) and replacement or non-replacement with suc as formula the conjugative monomer unit shown in (13-2),
(in the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously), wherein,, have structure with formula (14) expression in conjunction with the base of above-mentioned each monomeric unit:
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In addition, preferably contain in the high-molecular copolymer of metal complex, contain above-mentioned formula (1)～(12) represented any metal complex monomeric unit, replacement or non-replacement with the conjugative monomer unit shown in the formula (13-2) and the branched structure monomeric unit of replacement or non-replacement
(in the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously), wherein,, have structure with formula (14) expression in conjunction with the base of above-mentioned each monomeric unit:
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In addition, in the above-mentioned high-molecular copolymer that contains metal complex, replace or the branched structure monomeric unit of non-replacement is preferably selected from the branched structure monomeric unit shown in the formula (15).
(in the formula, a plurality of Y represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the position of substitution bonded substituting group with the phenyl ring of branched structure skeleton; And p is the integer of expression 0～4).
In addition, the invention provides a kind of polymer composition, it is characterized in that, the above-mentioned high-molecular copolymer that contains metal complex is mixed in conjugation or the unconjugated polymkeric substance.
In addition, the invention provides a kind of organic electroluminescent device, it is to utilize above-mentioned high-molecular copolymer that contains metal complex or above-mentioned polymer composition to make.
The Japanese patent application laid of content of the present invention and on June 18th, 2003 application is willing to that the theme of being put down in writing in 2003-173799 number, 2003-173874 number, 2003-173933 number and 2003-173986 number is relevant, can be with among its summary of the invention introducing the present invention.
Embodiment
In organic EL, need to change the energy level of lowest excited state from the extremely red phosphorescence of blueness if will obtain.In addition, usually the life-span of excited triplet state state is longer than the life-span of excited singlet state, therefore might be because molecule rests on higher-energy state for a long time, thereby caused and the reaction of peripheral material, the structural changes of molecule self, the reaction between the exciton etc., so the driving life-span of phosphorescence luminous element in the past is short.
Therefore, the present inventor finds after carrying out various researchs, the high-molecular copolymer that contains the metal complex monomeric unit shown in following formula (1)～(12) can become the phosphorescent light-emitting materials that can send the phosphorescence from the blueness to the redness and have the long driving life-span.
Formula (1)～(12):
B：＞O，＞S，＞C＝O，＞SO
2，＞CR
2
(in the formula, M is iridium (Ir), rhodium (Rh), ruthenium (Ru), osmium (Os), palladium (Pd) or platinum (Pt); N is 1 or 2; Ring A is the ring compound that contains with M bonded nitrogen-atoms; X
1～X
7And R represents respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8With-NR
9R
10Substituting group, R wherein
1～R
10Represent hydrogen atom separately respectively, halogen atom, cyano group (cyano), nitro, carbon number is 1～22 a straight chain, part or all of hydrogen atom on ring-type or branched-chain alkyl or these bases replaced by halogen atom and halogen-substituted alkyl, carbon number is 6～30 a aryl (aryl), carbon number is the part of 2～30 heteroaryl or the carbon number aralkyl (aralkyl) that is 7～30 or the hydrogen atom on these bases or is all replaced the halogen substituted aryl that gets by halogen atom, the halogen substituted heteroaryl, the halogen substituted aralkyl; R
1～R
10Can be separately identical, also can be difference, X
1～X
7Can be separately identical, also can be difference; Ring A can have and use X
1-X
7The identical substituting group of group of definition; Ring C is incorporated into M's and in conjunction with basic bonded compound; Ring C can have and use X
1-X
7The identical substituting group of group of definition).X at the metal complex monomeric unit
1～X
7, the R among the R
1～R
10Can have substituting group, substituting group for example is halogen atom, cyano group, aldehyde radical (aldehyde), amino, alkyl, alkoxyl group (alkoxy), alkylthio (alkylthio), carboxyl (carboxyl), sulfonic group, nitro or the like.These substituting groups can be further by replacements such as halogen atom, methyl.
Below be with X
1～X
7, the substituent example represented of R, but the present invention is not limited to this.
-R
1It for example is hydrogen atom, fluorine atom, the chlorine atom, bromine atoms, halogen atoms such as iodine atom, cyano group, nitro, methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, the tertiary butyl, cyclobutyl, amyl group, isopentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, nonyl, decyl, phenyl, tolyl (tolyl), xylyl (xylyl), 2,4,6-trimethylphenyl (mesityl), cumenyl (cumenyl), phenmethyl, styroyl (phenethyl), the methylbenzene methyl, diphenyl methyl, styryl (styryl), cinnamyl (cinnamyl), the biphenyl residue, the terphenyl residue, naphthyl (naphthyl), anthryl (anthryl), fluorenyl (fluorenyl), the furans residue, the thiophene residue, pyrroles's residue (pyrrole) oxazole residue (Oxazole), thiazole residue (thiazole), imidazoles residue (imidazole), the pyridine residue, pyrimidine residue (pyrimidine), pyrazine residue (pyrazine), three zin residues (triazine), the quinoline residue, quinoxaline residue (quinoxaline) or these are by fluorine atom, the chlorine atom, bromine atoms, the halogen that iodine atom etc. replace replaces body etc.
-OR
2For example be hydroxyl, methoxyl group (methoxy), oxyethyl group, propoxy-, butoxy, tert.-butoxy, octyloxy, uncle's octyloxy, phenoxy group, 4-tertiary butyl phenoxy group, 1-naphthyloxy, 2-naphthyloxy, 9-anthracene oxygen base (anthroxyl) etc.
-SR
3For example be sulfydryl (mercapto), methylthio group, ethylmercapto group, uncle's butylthio, own sulfenyl, hot sulfenyl, thiophenyl, 2-methylbenzene sulfenyl, 4-tert.-butylbenzene sulfenyl etc.
-OCOR
4For example be methanoyl (formyloxy), acetoxyl group (acetoxy), benzoyloxy (benzoyloxy) etc.
-COOR
5For example be carboxyl, methoxycarbonyl, ethoxycarbonyl, tertbutyloxycarbonyl, carbobenzoxy, naphthalene oxygen carbonyl etc.
-SiR
6R
7R
8For example be silyl, trimethyl silyl, triethylsilyl, triphenyl silyl etc.
NR
9R
10For example be amino, N-methylamino, N-ethylamino-, N, N dimethylamine base, N, N dimethylamine base, N, N-diisopropylamino, N, N-dibutyl amino, N-phenmethyl amido, N, N-diphenyl-methyl amido, N-phenyl amido, N, N-phenylbenzene amido etc.
Employed in the present invention metal complex can be phosphorescent, and minimum excited state may be MLCT (the metal-to-ligand charge transfer) excited state of triplet state, or π-π * excited state.Can produce phosphorescence during from these status transitions to ground state.
The phosphorescence quantum yield of luminescent material of the present invention can reach 0.1～0.9 higher value, and phosphorescent lifetime is 1～60 μ s.Short phosphorescent lifetime is the condition that makes the luminous efficiency high efficiency when making organic EL.That is, when phosphorescent lifetime was long, the molecular ratio regular meeting that is in excited triplet state became many, and under high current density, the luminous efficiency of burying in oblivion (annihilation) based on T-T can step-down.The high-molecular copolymer that contains metal complex of the present invention is a kind of material that is suitable as the luminescent material of organic EL, because it has high phosphorescence luminous efficiency and short luminescent lifetime.
In addition, the high-molecular copolymer that contains metal complex of the present invention can be by changing the substituting group of the metal complex monomeric unit shown in above-mentioned formula (1)～(12), change the energy level of lowest excited state, as the organic EL luminescent material that sends the light from the blueness to the redness.
In the metal complex monomeric unit shown in above-mentioned formula (1)～(12), M is iridium preferably.
In addition, ring A preferably has any ring compound of structure as follows, and preferably can have and use X
1～X
7(following with substituent X
nExpression) identical substituent pyridine (pyridine), quinoline, benzoxazole, benzothiazole, benzoglyoxaline, benzotriazole, imidazoles, pyrazoles (pyrazole), oxazole, thiazole, triazole, benzopyrazoles, triazine or isoquinoline 99.9, more preferably pyridine, quinoline or the isoquinoline 99.9 of group of definition.
(in the formula, Z
1～Z
6Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8With-NR
9R
10Substituting group, R wherein
1～R
10Represent hydrogen atom separately respectively, halogen atom, cyano group (cyano), nitro, carbon number is 1～22 a straight chain, part or all of hydrogen atom on ring-type or branched-chain alkyl or these bases replaced by halogen atom and halogen-substituted alkyl, carbon number is 6～30 a aryl (aryl), carbon number is the part of 2～30 heteroaryl or the carbon number aralkyl (aralkyl) that is 7～30 or the hydrogen atom on these bases or is all replaced the halogen substituted aryl that gets by halogen atom, the halogen substituted heteroaryl, the halogen substituted aralkyl; R
1～R
10Can be separately identical, also can be difference, Z
1～Z
6Can be separately identical, also can be difference).In addition, R
1～R
10Also can have substituting group, these substituting groups for example are halogen atom, cyano group, aldehyde radical, amino, alkyl, alkoxyl group, alkylthio, carboxyl, sulfonic group, nitro etc., and these substituting groups can be further by replacements such as halogen atom, methyl.
In addition, as the ring C of another dentate that is incorporated into metal M, be to have and use X
1～X
7Identical substituent two dentates of group of definition, it forms ring with the metal M combination.Ring C preferably has any compound of structure shown below.
W be by with the base of divalent～6 valencys of other monomeric unit reaction formation high-molecular copolymer, preferably divalent or 3 valencys.W for example is and following X
1～X
8Identical substituting group, and be can with combine the base of basic bonded divalent shown in the formula (14) to 6 valencys.
In the formula, X
1～X
8Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8,-NR
9R
10Substituting group, R wherein
1～R
10Represent hydrogen atom separately respectively, halogen atom, cyano group (cyano), nitro, carbon number is 1～22 a straight chain, part or all of hydrogen atom on ring-type or branched-chain alkyl or these bases replaced by halogen atom and halogen-substituted alkyl, carbon number is 6～30 a aryl (aryl), carbon number is the part of 2～30 heteroaryl or the carbon number aralkyl (aralkyl) that is 7～30 or the hydrogen atom on these bases or is all replaced the halogen substituted aryl that gets by halogen atom, the halogen substituted heteroaryl, the halogen substituted aralkyl; R
1～R
10Can be separately identical, also can be difference, X
1～X
8Can be separately identical, also can be difference.In addition, R
1～R
10Also can have substituting group, these substituting groups for example are halogen atom, cyano group, aldehyde radical, amino, alkyl, alkoxyl group, alkylthio, carboxyl, sulfonic group, nitro etc., and these substituting groups can be further by replacements such as halogen atom, methyl.(detailed description of the synthetic method of metal complex monomeric unit)
Below describe the synthetic method that is used for monomeric unit of the present invention in detail with concrete example.
At the metal complex monomeric unit that uses in the high-molecular copolymer of metal complex that contains of the present invention, can be by various known synthetic method manufacturings.For example: can use to be recorded in S.Lamansky etc., the method for J.Am.Chem.Soc.2001.123..Be example with the iridium complex compound monomeric unit below, the example of the synthetic route of the metal complex monomeric unit shown in formula (1)～(12) of having represented to use in the present invention (ring A is the situation of substituted pyridines).In addition, though explanation herein is relevant with (2) of table 1, other compound also can use the same method synthetic.
(dentate L
1Synthetic)
(synthesizing of iridium complex compound monomeric unit)
At this, L
2Be the compound that is incorporated into metal M (under the above-mentioned situation, being iridium), be with in conjunction with basic bonded ring C compound.
Preferred metal complex monomeric unit among the present invention is below described.
For example, in the metal complex monomeric unit shown in above-mentioned (1)～(6), under the situation that will obtain blue emitting material, viewpoint from the short wavelengthization that helps emission wavelength, preferably at least one in substituent X n or ring definition that A the had substituting group identical with Xn is halogen atom, cyano group or halogen-substituted alkyl, more preferably fluorine atom, chlorine atom, cyano group or trifluoromethyl, more preferably fluorine atom or trifluoromethyl, best is fluorine atom.In substituent X n or ring definition that A the had substituting group identical with Xn at least one though in most cases other Xn is a hydrogen atom, also can be other substituting group under above-mentioned any substituent situation.X for example
7Preferably alkyl or halogen-substituted alkyl.
In addition, for example, in the metal complex monomeric unit shown in above-mentioned (1)～(6), arrive in desirable green under the situation of red luminescent material, from can easily controlling the viewpoint of green illuminant colour to redness, at least one in the definition that substituent X n or ring A the have substituting group identical with Xn be preferably-R ,-OR or-SR.In substituent X n or the definition that has of the ring A substituting group identical with Xn at least one be under above-mentioned any substituent situation, though other Xn of most cases is a hydrogen atom, also can be other substituting group.X for example
7Preferably alkyl, aryl or heteroaryl.
In addition, for example, in the metal complex monomeric unit shown in above-mentioned (7)～(12), under the situation that will obtain blue emitting material, preferably use B be＞C=O or＞SO
2Compound.In addition, to obtain green under the situation of red illuminating material, B preferably＞O,＞S or＞CR
2From obtaining the viewpoint of blue-light-emitting look, in substituent X n or the definition that has of the ring A substituting group identical with Xn at least one is preferably halogen atom, cyano group or halogen-substituted alkyl, more preferably fluorine atom, chlorine atom, cyano group or trifluoromethyl, more preferably fluorine atom or trifluoromethyl, best is fluorine atom.Perhaps, from can easily controlling the viewpoint of blue illuminant colour to redness, be preferably-R ,-OR or-SR.In substituent X n or the definition that has of the ring A substituting group identical with Xn at least one be under above-mentioned any substituent situation, though other Xn of most cases is a hydrogen atom, also can be other substituting group.
In the metal complex shown in above-mentioned (1)～(6), from easy synthetic viewpoint, the metal complex shown in preferred formula (1) or the formula (4).In the metal complex shown in above-mentioned (7)～(12), from easy synthetic viewpoint, the metal complex shown in preferred formula (8) or the formula (11).
Object lesson as metal complex can illustrate following compound, but is not limited to this.
Table 1
Table 2
Table 3
In addition, as the object lesson of metal complex monomeric unit of the present invention, can enumerate the compound that the ring C in the compound that above-mentioned table 1～table 3 is put down in writing replaces with following dentate.
The high-molecular copolymer of containing metal coordination compound of the present invention contains with any metal complex monomeric unit of above-mentioned formula (1)～(12) expression and arylidene (arylene) and/or the branched structure monomeric unit of heteroarylidene monomeric unit, replacement or non-replacement and unitary one or more monomeric units of conjugative monomer of replacement or non-replacement of quinoline (quinoline) monomeric unit, replacement or the non-replacement that are selected from replacement or non-replacement.
As replacing or arylidene (arylene) and/or the branched structure monomeric unit of heteroarylidene monomeric unit, replacement or non-replacement and the conjugative monomer unit of replacement or non-replacement of quinoline (quinoline) monomeric unit, replacement or the non-replacement of non-replacement, can use the monomeric unit that in optimal way shown in following [1]～[4], illustrates.
In the high-molecular copolymer of containing metal coordination compound of the present invention, can use the combination base of explanation in following [1] as base in conjunction with various monomeric units.
The high-molecular copolymer of containing metal coordination compound of the present invention preferably contains each above-mentioned monomer component at least.Each monomeric unit can irregularly be contained in as in random copolymers in the multipolymer, perhaps also can be as block (block) multipolymer, grafting (grafting) multipolymer, and part, part certain monomers unit is present in the multipolymer.In addition, each monomeric unit that constitutes above-mentioned multipolymer can be a kind of monomeric unit, also can be the combination of two or more monomeric unit.
The following describes the optimal way of the high-molecular copolymer of containing metal coordination compound of the present invention.The high-molecular copolymer of [I] containing metal coordination compound, contain with any metal complex monomeric unit, replacement or the non-replacement of formula (1)～(12) expressions with quinoline (quinoline) monomeric unit of formula (13-1) expression and the arylidene (arylene) and/or the heteroarylidene monomeric unit of replacement or non-replacement.
(in the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, but these substituting groups be can be separately identical, also can be different, as to be incorporated into the position of substitution in quinoline residue substituting groups; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene (Arylene); E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-) m-O-(m is 1～3 integer) combine with the divalent of-Q-base [in the formula, W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, Ar ' is an arylidene, Ra ' separately respectively expression be selected from the base of alkylidene group, arylidene and alkylidene group/arylidene mixed base, Het ' is a heteroarylidene, Q is the divalent base that contains level Four carbon]).
Base in conjunction with above-mentioned each monomeric unit is preferably basic with the combination of formula (14) expression.
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
Quinoline monomeric unit shown in the formula of Shi Yonging (13-1) can use separately in the present invention, perhaps also can be used in combination.
In the quinoline monomeric unit shown in the formula (13-1), a plurality of V represent-R
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8In addition, substituting group V is substituted under a plurality of situations, and these V can be identical substituting groups, also can be mutually different substituting group.A represents 0～3 integer respectively independently.
On the other hand, as the R among the substituting group V
1～R
8, can represent respectively separately that carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl.These bases for example are methyl, ethyl, propyl group, cyclopropyl, butyl, isobutyl-, cyclobutyl, amyl group, isopentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, nonyl, carbon numbers such as decyl are 1～22 straight chained alkyl, the alkyl of cyclic alkyl or side chain, and phenyl, naphthyl, anthryl (anthracenyl), the biphenyl residue, the terphenyl residue, the furans residue, the thiophene residue, pyrroles's residue oxazole residue, the thiazole residue, the imidazoles residue, the pyridine residue, the pyrimidine residue, the pyrazine residue, three zin residues, the quinoline residue, carbon numbers such as quinoxaline residue are 2～30 aryl or heteroaryl.
In addition, substituting group V can have substituting group.As the substituting group that V has, can enumerate above-mentioned with R
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8The substituting group of expression and with-NR
9R
10(R
9, R
10Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～20 aryl or heteroaryl) expression substituting group.Exist under a plurality of substituent situations, each substituting group can be identical, also can be different.
In the monomeric unit of formula of the present invention (13-1), Va is independent separately, and with regard to solvability and thermotolerance, being preferably a, to equal 0 be unsubstituted structure, perhaps by with-R
1The V of expression is specially alkyl, the direct substitution structure of aryl.In addition, with regard to the substituting group number, a equals 0 and does not promptly replace or a is 1 or 2 o'clock, is preferred from the viewpoint of polymerisation reactivity.In addition, aryl phenyl preferably.
In addition, in the quinoline monomeric unit of formula (13-1), D is each independently singly-bound or arylidene.D is arylidene preferably, with the viewpoint of good polymerisation reactivity, preferably neighbour-penylene ,-penylene, right-penylene.
E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-) m-O-(m is 1～3 integer) combines base with the divalent of-Q-.Above-mentioned W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, Ar ' is an arylidene, Ra ' separately respectively expression be selected from the base of alkylidene group, arylidene and alkylidene group/arylidene mixed base, Het ' is a heteroarylidene, Q is the divalent base that contains level Four carbon.Wherein E preferably singly-bound ,-O-,-Ar '-or-Ra '-O-Ra ', from the viewpoint of polymerisation reactivity, E is preferably phenyl residues, luxuriant and rich with fragrance residue, fluorenes residue, carbazole (carbazole) residue, biphenyl residue, diphenyl ether residue.
In addition to these, as alkylidene group, arylidene or heteroarylidene and the Q in the divalent base of representing with D or E, can enumerate from as the R the above-mentioned substituting group V
1-R
8The substituting group enumerated of example in removed the divalent base of a hydrogen atom.
In formula (13-1), the divalent base of representing with D or E can have substituting group.As the substituting group that D or E have, can enumerate with above-mentioned R
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Or-NR
9R
10The substituting group of expression.Exist under a plurality of substituent situations, these substituting groups can be identical or inequality.
The object lesson of the quinoline monomeric unit in the formula (13-1) can be following compound, but is not limited to this.
In above-mentioned quinoline monomeric unit, substituent R can be with above-mentioned R
1,-OR2 ,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8Or-NR
9R
10The substituting group of expression.In addition, R can be a hydrogen atom.Substituent R can be identical or inequality.
In addition, as the arylidene that is used in replacement of the present invention or non-replacement and/or the heteroarylidene monomeric unit base of divalent preferably, can enumerate benzene, biphenyl, terphenyl, naphthalene (naphthalene), anthracene, tetracene (tetracene), fluorenes, luxuriant and rich with fragrance, pyrene (pyrene), 1,2-benzophenanthrene (chrysene), pyridine, pyrazine, isoquinoline 99.9, acridine (acridine), phenanthroline (phenanthroline), furans, the pyrroles, thiophene oxazole oxadiazole, thiadiazoles, triazole benzoxazole Ben Bing oxadiazole, diazosulfide, thionaphthene, Er Ben oxadiazole, diazosulfide, the phenylbenzene diazole, phenylbenzene thiadiazoles etc., and as arylidene and/or heteroarylidene monomeric unit, these can use separately or in conjunction with a plurality of uses.In addition, arylidene and/or heteroarylidene monomeric unit can use separately, also can be used in combination.
Arylidene and/or heteroarylidene monomeric unit can have substituting group.Substituting group for example is with above-mentioned R
1,-OR
2,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8Or-NR
9R
10The substituting group of expression etc.Exist under a plurality of substituent situations, a plurality of substituting groups can be identical or inequality.
R
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl.These bases for example are methyl, ethyl, propyl group, cyclopropyl, butyl, isobutyl-, cyclobutyl, amyl group, isopentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, nonyl, carbon numbers such as decyl are 1～22 straight chained alkyl, the alkyl of cyclic alkyl or side chain and phenyl, naphthyl, anthryl, the biphenyl residue, the terphenyl residue, the furans residue, the thiophene residue, pyrroles's residue oxazole residue, the thiazole residue, the imidazoles residue, the pyridine residue, the pyrimidine residue, the pyrazine residue, three zin residues, the quinoline residue, carbon numbers such as quinoxaline residue are 2～30 aryl or heteroaryl.Substituting group with arylidene and/or heteroarylidene monomeric unit can also have substituting group.
Substituting group that arylidene of the present invention and/or heteroarylidene monomeric unit have is independent respectively, and with regard to solvability and thermotolerance, be preferably unsubstituted structure and be hydrogen atom, or by with-R
1The direct substitution structure of alkyl, aryl, heteroaryl of expression or by with-OR
2The structure that the alkoxyl group of expression, aryloxy (aryloxy), heteroaryloxy replace.In addition, from the viewpoint of polymerisation reactivity, being preferably hydrogen atom is that unsubstituted situation and substituting group number are 1 to 3 structure.In addition, preferably replace as aryl or phenyl, replacement or the unsubstituted fluorenyl etc. of non-replacement.In addition, select De Shi oxadiazole base, Ben oxadiazole base, phenyl thiadiazolyl group, diazosulfide base etc. as heteroaryl You.
Can represent the example that some are representative with following structural formula.
The substituent R of these arylidene and/or heteroarylidene monomeric unit is respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately hydrogen atom, carbonatoms are the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl.That these substituting groups can be separately is identical, also can be difference, but and is the substituting group that is incorporated into the position of substitution in arylidene and/or the heteroarylidene skeleton.
In these substituting groups, R is respectively independent, and being expressed as hydrogen atom is unsubstituted structure, perhaps with-R
1The structure that shown alkyl, aryl, heteroaryl are direct substitution or with-OR
2Hydroxyl, alkoxyl group, aryloxy, the heteroaryloxy of expression, these are preferred groups with regard to solvability and thermotolerance.
In the high-molecular copolymer [I] of containing metal coordination compound of the present invention, preferably represent with formula (14) in conjunction with the base of each monomeric unit.
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-the divalent base, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In above-mentioned formula (14), b represented singly-bound at 0 o'clock.As these in conjunction with base with regard to synthetic simplicity preferably singly-bound or-O-.As-R-O-R-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2In R, from giving deliquescent viewpoint, preferably carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, with regard to the viewpoint of polymerisation reactivity, is preferably the alkyl that carbonatoms is 1～6 a straight chain.
At least the monomeric unit that contains above-mentioned three components at the high-molecular copolymer [I] of containing metal coordination compound of the present invention, in case of necessity, as [comonomer unit] beyond these monomeric units, can contain the monomeric unit with triphenylamine skeleton of replacement or non-replacement.Has the monomeric unit of triphenylamine skeleton as these, can enumerate triphenylamine, N-(4-butyl phenyl)-N, N-diphenylamine, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-[1,1 '-biphenyl]-4,4 '-diamines, N, N '-two (3-aminomethyl phenyl)-N, N '-two (2-naphthyl)-[1,1 '-biphenyl]-4,4 '-diamines etc.Also having, as the group that can be replaced in these aromatic nucleus, can be that carbon number is 1～22 alkyl, alkoxyl group etc.
In whole monomeric unit total amounts of the high-molecular copolymer [I] of containing metal coordination compound of the present invention, the shared mole fraction of metal complex monomeric unit preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.The metal complex monomeric unit is if be less than 0.1%, and its luminescent chromaticity meeting variation can reduce above 30% o'clock glorious degrees.
In whole monomeric unit total amounts of the high-molecular copolymer [I] of containing metal coordination compound of the present invention, the shared mole fraction of quinoline monomeric unit preferably 1～70%, better is 3～65%, the best is 5～50%.The quinoline monomeric unit is less than 1% o'clock glorious degrees can be reduced, and surpassing 70% o'clock luminescent chromaticity can variation.
In whole monomeric unit total amounts of the high-molecular copolymer [I] of containing metal coordination compound of the present invention, the shared mole fraction in arylidene and/or heteroarylidene unit preferably 1～99%, better is 3～97%, the best is 5～95%.Arylidene and/or heteroarylidene monomeric unit amount are less than 1% o'clock its glorious degrees and can reduce, and surpassing 99% o'clock luminescent chromaticity can variation.
Can copolymerization in the mole fraction of the monomeric unit with triphenylamine skeleton in the whole monomeric unit total amounts of the polymkeric substance high-molecular copolymer [I] of containing metal coordination compound of the present invention, replacement or non-replacement, preferably 0～30%.
The high-molecular copolymer of containing metal coordination compound of the present invention can utilize the known synthetic method manufacturing of various art technology philtrums.For example, when not in conjunction with each monomeric unit basic, can adopt the method that to report people such as (Bulletin of the ChemicalSociety of Japan) 51 volumes No. 7 2091 pages (1978) and M.Zembayashi in tetrahedron letter (Tetrahedron Letters) 47 volumes 4089 pages (1977), to put down in writing in the chemical association of Japan as people such as T.Yamamoto.Particularly, for the manufacturing of multipolymer, Suzuki institute's method of reporting in synthetic information (Synthetic Communications) 11 volumes No. 7 513 pages (1981) be the method for generally using always.In this reaction, between aromatic boric acid (boronic acid) derivative and aromatic halide, produce palladium (Pb) catalysis thinner cross coupling (cross-coupling) reaction (being commonly referred to as " suzuki reaction "), by the reaction that is used to corresponding aromatic series lopps is bonded to each other, can make the high-molecular copolymer of containing metal coordination compound of the present invention.
In addition, usually use (II) the soluble palladium compound of salt or Pd (0) complex compound kenel of Pd (palladium) in this reaction.With the aromatic series reactant as benchmark, the Pd (PPh of 0.01～5 molar percentage
3)
4The Pd (OAc) of (four triphen phosphorus base palladiums), 3 grades of phosphine dentates (phosphine ligand)
2(diacetyl palladium) complex compound and PdCl
2(dppf) (dppf=1,1 '-two (hexichol phosphorus base) ferrocene, 1,1 '-bis (diphenylphosphino) ferrocene) complex compound is general preferred Pd source.Also using alkali (base) in this reaction, is the best with water-soluble alkali acid carbonate (alkali carbonate) or supercarbonate (bicarbonate).And, can use the reaction in the alternate moving catalyst promotion non-polar solvent.Can use N as solvent, and dinethylformamide (N, N-dimethylformamide), toluene (toluene), glycol dimethyl ether (dimethoxyethane), tetrahydrofuran (THF) (tetrahydrofuran) etc.
Under the situation of polymkeric substance of the present invention [I], particularly, can be by hypoboric acid ester and dibromo metal complex derivatives monomer, dibromo arylidene and/or the dibromo heteroarylidene monomer that makes the quinoline of representing with following formula, exist down in Pd (0) catalyzer, utilize water-soluble alkali to carry out copolymerization and make.
Perhaps
(R ' is low alkyl groups such as methyl, ethyl, propyl group in the formula, or 2 R ' combine and form the low-grade alkylidene such as ethylidene, propylidene of ring, and V and D, E and a are as above-mentioned definition).
When the base in conjunction with each monomeric unit is under the situation of O, can be in the presence of alkali, following monomer is reacted and make the high-molecular copolymer of containing metal coordination compound of the present invention, described monomer is difluoro-quinoline monomer and dihydroxyl metal complex derivatives monomer and dihydroxyl arylidene and/or the dihydroxyl heteroarylidene monomer for being put down in writing in the Japanese kokai publication hei 9-136954 communique for example, dibromo metal complex derivatives monomer and dibromo arylidene and/or dibromo heteroarylidene monomer and dihydroxyl quinoline monomer, or two bromoquinoline monomer and dibromo arylidene and/or dibromo heteroarylidene monomer and dihydroxyl metal complex derivatives monomer.In this reaction, be the reaction that in the presence of the alkali that can make the dihydroxy compound deprotonation, is used to make the high-molecular copolymer of containing metal coordination compound of the present invention.Such alkali is basic metal and alkaline earth metal carbonate and oxyhydroxide, and the example that can enumerate has salt of wormwood, potassium hydroxide, yellow soda ash, sodium hydroxide etc.When the acidity of dihydroxy compound low and can't fully carry out deprotonation with sodium hydroxide the time, also can use for example metal hydride, butylation lithium (butyllithium), sodium amide amination metals such as (sodium amide) or the like such as sodium hydride of stronger alkali.When such alkali and dihydroxy compound reaction, can generate water, can utilize component distillation that this water is removed.
In addition, on the high-molecular copolymer [I] of containing metal coordination compound of the present invention, can also other monomer of copolymerization, as these other dihydroxyl monomer example, can enumerate isopropylidene (propylidene) biphenol (dihydroxyphenyl propane), 1,2-two (4-hydroxyphenyl) ethane, two (4-hydroxyphenyl) methane, N, two (4-the hydroxyphenyl)-N-phenyl amine of N-, N, N '-two (4-hydroxyphenyl)-N, N '-two (3-tolyl)-[1,1 '-biphenyl]-4,4 '-diamines etc.
The high-molecular copolymer of [II] containing metal coordination compound, contain with any metal complex monomeric unit, replacement or the non-replacement of above-mentioned formula (1)～(12) expressions with quinoline (quinoline) monomeric unit of formula (13-1) expression and the branched structure monomeric unit of replacement or non-replacement.
(in the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in the quinoline residue; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene (Arylene); E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-) m-O-(m is 1～3 integer) combine with the divalent of-Q-base [W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, and Ar ' is an arylidene, and Ra ' is expressed as the base that is selected from alkylidene group, arylidene and alkylidene group/arylidene mixed base separately respectively, Het ' is a heteroarylidene, and Q is the divalent base that contains level Four carbon]).
Base in conjunction with above-mentioned monomeric unit is preferably basic with the combination of formula (14) expression.
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer)
That uses in the present invention is identical with quinoline monomeric unit in [I] with the quinoline monomeric unit shown in the formula (13-1).
In addition, be used in the branched structure monomeric unit of replacement of the present invention or non-replacement, preferably have the unit of the above branched structure of 3 valencys, better is the unit with branched structure of 3 valencys or 4 valencys.Monomeric unit as branched structure preferably for example is with the structure shown in the formula (15).
Perhaps
These branched structure monomeric units can use separately, also can use the combination more than 2 kinds.In the branched structure monomeric unit of formula (15), substituting group Y represents respectively to be selected from-R independently
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group of the position of substitution that is incorporated into the phenyl ring of branched structure skeleton; And p is the integer of expression 0～4.P is preferably 0-2.
On the other hand, the R in substituting group Y
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chained alkyl, cyclic alkyl or side chain, or carbonatoms is 2～30 aryl or heteroaryl.These bases for example are methyl, ethyl, propyl group, cyclopropyl, butyl, isobutyl-, cyclobutyl, amyl group, isopentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, nonyl, carbon numbers such as decyl are 1～22 straight chained alkyl, the alkyl of cyclic alkyl or side chain and phenyl, naphthyl, anthryl, the biphenyl residue, the terphenyl residue, the furans residue, the thiophene residue, pyrroles's residue oxazole residue, the thiazole residue, the imidazoles residue, the pyridine residue, the pyrimidine residue, the pyrazine residue, three zin residues, the quinoline residue, carbon numbers such as quinoxaline residue are 2～30 aryl or heteroaryl.
In addition, substituting group Y can have substituting group.As substituting group, can enumerate above-mentioned with R with Y
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8The substituting group of expression and with-NR
9R
10(R
9, R
10Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～20 aryl or heteroaryl) expression substituting group.Exist under most substituent situations, these substituting groups can be identical or different.
In these substituting groups, be to represent independently that respectively it is unsubstituted structure that p equals 0 as Yp, or by with-R
1The Y of expression is the direct substitution structure of alkyl, and these are preferred with regard to polymerisation reactivity and thermotolerance.In addition, with regard to the substituting group number, from the viewpoint of polymerisation reactivity, preferred unsubstituted situation is that to equal 0 situation and p be 1 situation to p.
In the high-molecular copolymer [II] of containing metal coordination compound, basic identical with the combination in above-mentioned [I] with the base in conjunction with each monomeric unit of formula (14) expression.
At least the monomeric unit that contains 3 kinds of above-mentioned compositions in the high-molecular copolymer of containing metal coordination compound of the present invention [II], the monomeric unit with triphenylamine skeleton that can contain in case of necessity, replacement or non-replacement as [comonomer unit] beyond these monomeric units.As these monomeric units with triphenylamine skeleton can use with above-mentioned [I] in the same monomeric unit of the monomeric unit with triphenylamine skeleton.
In addition, the monomeric unit that in the high-molecular copolymer [II] of containing metal coordination compound of the present invention, contains 3 kinds of above-mentioned compositions at least, the arylidene and/or the heteroarylidene monomeric unit that can contain in case of necessity, replacement or non-replacement as [comonomer unit] beyond these monomeric units.As the monomeric unit of the arylidene of these replacements or non-replacement and/or heteroarylidene can use with above-mentioned [I] in arylidene and/or the same monomeric unit of heteroarylidene monomeric unit.
In whole monomeric unit total amounts of the high-molecular copolymer [II] of containing metal coordination compound of the present invention, the shared mole fraction of metal complex monomeric unit preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.Its luminescent chromaticity meeting variation that the metal complex monomeric unit is less than at 0.1% o'clock, surpassing 30% o'clock glorious degrees can reduce.
In whole monomeric unit total amounts of the high-molecular copolymer [II] of containing metal coordination compound of the present invention, the shared mole fraction of quinoline monomeric unit preferably 1～70%, better is 3～65%, the best is 5～50%.The quinoline monomeric unit is less than at 1% o'clock, and its glorious degrees can reduce, and surpassing 70% o'clock luminescent chromaticity can variation.
In whole monomeric unit total amounts of the high-molecular copolymer [II] of containing metal coordination compound of the present invention, replace or mole fraction that the branched structure monomeric unit of non-replacement is shared preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.Its luminescent chromaticity meeting variation that the branched structure monomeric unit is less than at 0.1% o'clock, surpassing 30% o'clock glorious degrees can reduce.
But the replacement of copolymerization on the high-molecular copolymer [II] of containing metal coordination compound of the present invention or the arylidene and/or the heteroarylidene monomeric unit of the monomeric unit with triphenylamine skeleton, replacement or the non-replacement of non-replacement, mole fraction in whole monomeric unit sums of polymkeric substance, preferably 0～48%.
The high-molecular copolymer of containing metal coordination compound of the present invention [II] can adopt the synthetic method manufacturing identical with above-mentioned [I].
Under the situation of polymkeric substance of the present invention [II], for example under the situation of nothing in conjunction with the group of each monomeric unit, particularly, hypoboric acid ester that can be by making the quinoline of representing with following formula and dibromo metal complex derivatives monomer, tribromo branched structure derivative, exist down in Pd (0) catalyzer, utilize water-soluble alkali to carry out copolymerization and make.
Perhaps
(R ' is low alkyl groups such as methyl, ethyl, propyl group in the formula, or 2 R ' combine and form the low-grade alkylidene such as ethylidene, propylidene of ring, and V and D, E and a are as above-mentioned definition).
When the base in conjunction with each monomeric unit is under the situation of O, can be in the presence of alkali, following monomer is reacted and make the high-molecular copolymer of containing metal coordination compound of the present invention, described monomer is difluoro-quinoline monomer and dihydroxyl metal complex derivatives monomer and the trihydroxy-branched structure derivative of being put down in writing in the Japanese kokai publication hei 9-136954 communique, dibromo metal complex derivatives monomer and tribromo branched structure derivative and dihydroxyl quinoline monomer, or two bromoquinoline monomer and tribromo branched structure derivative and dihydroxyl metal complex derivatives monomer.
In addition, going up at the high-molecular copolymer [II] of containing metal coordination compound of the present invention can also other monomer of copolymerization, as these other dihydroxyl monomer for example can use with [I] in the identical monomer of dihydroxyl monomer.
The high-molecular copolymer of [III] containing metal coordination compound contains the conjugative monomer unit with formula (13-2) expression with any metal complex monomeric unit, replacement or the non-replacement of above-mentioned formula (1)～(12) expression.
(in the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously).
Base in conjunction with above-mentioned monomeric unit is preferably basic with the combination of formula (14) expression.
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, herein, R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
Use in the present invention with the conjugative monomer unit shown in the formula (13-2), can use separately, perhaps make up more than 2 kinds and use together.
In the monomeric unit of formula of the present invention (13-2), Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously.Ar
1With Ar
2Can be identical, also can be difference.In addition, under the situation that has a plurality of substituting group V to replace, these substituting groups can be identical or different substituting groups.
In formula (13-2), Ar
1With Ar
2Be the arylidene and/or the heteroarylidene of replacement or non-replacement.Arylidene and/or heteroarylidene as these replacements or non-replacement, the base of divalent preferably, it can be benzene, biphenyl, terphenyl, naphthalene, anthracene, tetracene, fluorenes, phenanthrene, pyrene, 1,2-benzophenanthrene, pyridine, pyrazine, quinoline, isoquinoline 99.9, acridine, phenanthroline, furans, pyrroles, thiophene, oxazole, oxadiazole, thiadiazoles, triazole, benzoxazole, Ben Bing oxadiazole, diazosulfide, thionaphthene, Er Ben oxadiazole, diazosulfide, phenylbenzene diazole, phenylbenzene thiadiazoles etc.Ar
1With Ar
2Can use separately, perhaps in conjunction with a plurality of uses.
On the other hand, substituting group V and R
1, R
2In R
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chained alkyl, cyclic alkyl or side chain, or carbonatoms is 2～30 aryl or heteroaryl.These bases for example are methyl, ethyl, propyl group, cyclopropyl, butyl, isobutyl-, cyclobutyl, amyl group, isopentyl, neo-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, suberyl, octyl group, nonyl, carbon numbers such as decyl are 1～22 straight chained alkyl, the alkyl of cyclic alkyl or side chain, and phenyl, naphthyl, anthryl, the biphenyl residue, the terphenyl residue, the furans residue, the thiophene residue, pyrroles's residue oxazole residue, the thiazole residue, the imidazoles residue, the pyridine residue, the pyrimidine residue, the pyrazine residue, three zin residues, the quinoline residue, carbon numbers such as quinoxaline residue are 2～30 aryl or heteroaryl.
In addition, substituting group V, R
1, R
2Can have substituting group again.As V, R
1And R
2The substituting group that has can be enumerated above-mentioned with R
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8The substituting group of expression, and with-NR
9R
10(R
9, R
10Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～20 aryl or heteroaryl) expression substituting group.Exist under most substituent situations, these substituting groups can be identical or different.
In the conjugative monomer unit of formula of the present invention (13-2), V, R
1, R
2Respectively independent, with regard to solvability and thermotolerance, preferably unsubstituted structure is that it is a hydrogen atom, perhaps with-R
1The direct substitution structure of alkyl, aryl, heteroaryl of expression is perhaps with-OR
2The structure that the alkoxyl group of expression, aryloxy, heteroaryloxy replace.In addition, with regard to the substituting group number, from the viewpoint of polymerisation reactivity, preferred a or b are 0 promptly to be 1～3 situation at the situation that does not contain replacement and a or b.In addition, preferably replace or unsubstituted phenyl, replacement or unsubstituted fluorenyl etc. as aryl.In addition, select De Shi oxadiazole base, Ben oxadiazole base, phenyl thiadiazolyl group, diazosulfide base etc. as heteroaryl You.
Ar
1With Ar
2Typical example can represent with following structural formula.
The substituent R of these arylidene and/or heteroarylidene is represented respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and is the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue.
In these substituting groups, R is respectively independent, and with regard to polymerisation reactivity and thermotolerance, preferred unsubstituted structure is that it is a hydrogen atom, perhaps with-R
1The direct substitution structure of alkyl, aryl, heteroaryl of expression is perhaps with-OR
2The structure that the hydroxyl of expression, alkoxyl group, aryloxy, heteroaryloxy replace.
In the high-molecular copolymer [III] of containing metal coordination compound of the present invention, basic identical with the combination in above-mentioned [I] with the base in conjunction with each monomeric unit of formula (14) expression.
The monomeric unit that in the high-molecular copolymer [III] of containing metal coordination compound of the present invention, contains above-mentioned 2 kinds of compositions at least, the monomeric unit with triphenylamine skeleton that can contain in case of necessity, replacement or non-replacement as [comonomer unit] beyond these monomeric units.These monomeric units with triphenylamine skeleton can use with above-mentioned [I] in the same monomeric unit of the monomeric unit with triphenylamine skeleton.
In whole monomeric unit total amounts of the high-molecular copolymer [III] of containing metal coordination compound of the present invention, the shared mole fraction of metal complex monomeric unit preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.Its luminescent chromaticity meeting variation that the metal complex monomeric unit is less than at 0.1% o'clock, surpassing 30% o'clock glorious degrees can reduce.
In whole monomeric unit total amounts of the high-molecular copolymer [III] of containing metal coordination compound of the present invention, the shared mole fraction in conjugative monomer unit preferably 70～99.9%, better is 75～99.5%, the best is 80～99%.The conjugative monomer unit is less than 70% o'clock its glorious degrees can be reduced, and surpassing 99.9% o'clock luminescent chromaticity can variation.
Also have, but copolymerization in the replacement of the high-molecular copolymer [III] of containing metal coordination compound of the present invention or the monomeric unit with triphenylamine skeleton of non-replacement, at the mole fraction of whole monomeric unit sums of polymkeric substance, preferably 0～49%.
The high-molecular copolymer of containing metal coordination compound of the present invention [III] can adopt the synthetic method identical with above-mentioned [I] to make.
Under the situation of polymkeric substance of the present invention [III], for example under the situation of nothing in conjunction with the group of each monomeric unit, particularly, the hypoboric acid ester that can be by making the conjugative monomer derivative of representing with following formula and/or the dibromo compound and the dibromo metal complex derivatives monomer of conjugative monomer derivative, exist down in Pd (0) catalyzer, utilize water-soluble alkali to carry out copolymerization and make.
Perhaps/and
(R is low alkyl groups such as methyl, ethyl, propyl group in the formula, or 2 R combine and form the low-grade alkylidene such as ethylidene, propylidene of ring, Ar
1, Ar
2, R
1, R
2, V, a, b, n, m, l be as above-mentioned definition).
When the base in conjunction with each monomeric unit is under the situation of O, can be in the presence of alkali, following monomer is reacted and make the high-molecular copolymer of containing metal coordination compound of the present invention, described monomer is difluoro conjugative monomer and dihydroxyl metal complex derivatives monomer, dibromo metal complex derivatives monomer and dihydroxyl conjugative monomer or dibromo conjugative monomer and the dihydroxyl metal complex derivatives monomer of being put down in writing in the Japanese kokai publication hei 9-136954 communique.
In addition, going up at the high-molecular copolymer [II] of containing metal coordination compound of the present invention can also other monomer of copolymerization, as these other dihydroxyl monomer for example can use with [I] in the identical monomer of dihydroxyl monomer.
The high-molecular copolymer of [IV] containing metal coordination compound, contain with any metal complex monomeric unit, replacement or the non-replacement of above-mentioned formula (1)～(12) expressions with the conjugative monomer unit and the replacement of formula (13-2) expression or divide the monomeric unit of the branched structure that replaces.
(in the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but and be the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously).
Group in conjunction with above-mentioned monomeric unit is preferably basic with the combination of formula (14) expression.
-(G)b- (14)
(in the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer).
In the present invention, can be identical with the conjugative monomer unit shown in the formula (13-2) with the conjugative monomer unit in above-mentioned [III].
In addition, as the monomeric unit of the branched structure that is used for replacement of the present invention or non-replacement, can use with above-mentioned [II] in the identical monomeric unit of monomeric unit of branched structure.
In the high-molecular copolymer [IV] of containing metal coordination compound, with the base in conjunction with each monomeric unit of formula (14) expression be with above-mentioned [I] in identical in conjunction with base.
The monomeric unit that in the high-molecular copolymer [IV] of containing metal coordination compound of the present invention, contains above-mentioned three components at least, the monomeric unit with triphenylamine skeleton that can contain in case of necessity, replacement or non-replacement as the thing [comonomer unit] beyond these monomeric units.As these monomeric units with triphenylamine skeleton can use with above-mentioned [I] in the same monomeric unit of the monomeric unit with triphenylamine skeleton.
In whole monomeric unit total amounts of the high-molecular copolymer [IV] of containing metal coordination compound of the present invention, the shared mole fraction of metal complex monomeric unit preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.Its luminescent chromaticity meeting variation that the metal complex monomeric unit is less than at 0.1% o'clock, surpassing 30% o'clock glorious degrees can reduce.
In whole monomeric unit total amounts of the high-molecular copolymer [IV] of containing metal coordination compound of the present invention, the shared mole fraction in conjugative monomer unit preferably 50～99.9%, better is 60～99.5%, the best is 75～99%.The conjugative monomer unit is less than 50% o'clock its glorious degrees can be reduced, and surpassing 99.9% o'clock luminescent chromaticity can variation.
In whole monomeric unit total amounts of the high-molecular copolymer [IV] of containing metal coordination compound of the present invention, replace or mole fraction that the branched structure monomeric unit of non-replacement is shared preferably 0.1～30%, better is 0.5～20%, the best is 1～10%.Its luminescent chromaticity meeting variation that the branched structure monomeric unit is less than at 0.1% o'clock, surpassing 30% o'clock glorious degrees can reduce.
But copolymerization is in the replacement of the high-molecular copolymer [IV] of containing metal coordination compound of the present invention or the monomeric unit with triphenylamine skeleton of non-replacement, the mole fraction in whole monomeric unit sums of polymkeric substance, preferably 0～48%.
The high-molecular copolymer of containing metal coordination compound of the present invention [IV] can adopt the synthetic method identical with above-mentioned [I] to make.
Under the situation of polymkeric substance of the present invention [IV], for example under the situation of nothing in conjunction with the group of each monomeric unit, particularly, the hypoboric acid ester that can be by making the conjugative monomer derivative of representing with following formula and/or the dibromo compound of conjugative monomer derivative and dibromo metal complex derivatives monomer, tribromo branched structure derivative, exist down in Pd (0) catalyzer, utilize water-soluble alkali to carry out copolymerization and make.
And/or
When the base in conjunction with each monomeric unit is under the situation of O, can be in the presence of alkali, following monomer is reacted and make the high-molecular copolymer of containing metal coordination compound of the present invention, described monomer is difluoro conjugative monomer and dihydroxyl metal complex derivatives monomer and the trihydroxy-branched structure derivative of being put down in writing in the Japanese kokai publication hei 9-136954 communique, dibromo metal complex derivatives monomer and tribromo branched structure derivative and dihydroxyl conjugative monomer, or dibromo conjugative monomer and tribromo branched structure derivative and dihydroxyl metal complex derivatives monomer.
In addition, going up at the high-molecular copolymer [IV] of containing metal coordination compound of the present invention can also other monomer of copolymerization, as these other dihydroxyl monomer for example can use with [I] in the identical monomer of dihydroxyl monomer.
The molecular weight of the high-molecular copolymer of containing metal coordination compound of the present invention is with 10,000～1, and 000,000 is good, and 30,000～800,000 for better.If less than 10,000, the ability that forms film (film) has the tendency of decline.If surpass 1,000,000, then solvability has the tendency of decline.
The high-molecular copolymer of containing metal coordination compound of the present invention can be as the active layer material of electroluminescent cell.So-called active coating is an irradiative layer (luminescent layer) when using in electric field, or is used to improve the injection of electric charge or the layer of movement of electric charges (electric charge injection layer or electric charge mobile layer).At this so-called electric charge is the negative or positive electric charge.
The thickness of active coating can be considered luminous efficiency etc. and does suitable setting, be good with 10～300nm, and 20～200nm is for better.When not enough 10nm, the tendency of generation pin hole film defects such as (pinhole) is then arranged, when surpassing 300nm, the tendency that then has characteristic to reduce.
Multipolymer of the present invention can use with the material mixing beyond these.In addition, used the electroluminescent cell of multipolymer of the present invention, can adopt the layer structure mutually stacked that contains above-mentioned multipolymer material in addition with the active coating that contains multipolymer of the present invention.As mixing the material that uses, material known such as hole injection and/or hole mobile material, electronics injection and/or electron migration material, luminescent material, bonding (binder) polymkeric substance are arranged with multipolymer of the present invention.No matter institute's blended material is that macromolecular material or low molecular material all can.
Can be used as that the hole is injected and/or the material of hole mobile material, for example be material such as aromatic amine derivant, triphenyl methane derivative, Stilbene (stilbene) based compound, hydrazone system (hydrazone) compound, carbazole based compound, high molecular aromatic amine, polyaniline (aniline), Polythiophene or these have been implemented the material of high molecular.Can be used as that electronics injects and/or the material of electron migration material material such as Shi oxadiazole derivative, benzoxazole derivative, benzoquinones (quinone) derivative, quinoline, quinoxaline derivatives, thiadiazoles derivative, benzothia (oxa) diazol derivatives, triazole derivative, metal-chelating (chelate) complex compound or these have been implemented the material of high molecular for example.Spendable luminescent material can be aromatic amine derivant oxadiazole derivative perylene (perylene) derivative, quinoline a word used for translation ketone (quinacridone) derivative, pyrazoline (pyrazoline) derivative, anthracene derivant, rubrene (rubrene) derivative, stilbene derivative, tonka bean camphor (coumarin) derivative, naphthalene derivatives, the metal-chelating complex compound, contain iridium or platinum and be the material such as metal complex of central metal and it has been implemented the material of high molecular, poly-fluorene derivatives, the polyphenylene vinylene derivative, polyphenylene derivatives, polymer materialss such as polythiofuran derivative.As the material that can be used as bonding polymer, as long as just can using of not obvious influencing characteristic for example can be used materials such as polystyrene, polycarbonate, polyarylether, polyacrylic ester, polymethacrylate, polysiloxane.
The high-molecular copolymer that contains metal complex of the present invention can use with the polymer composition that is mixed in conjugation or the non-conjugated polymeric thing.As conjugation that can be used for polymer composition or non-conjugated polymeric thing, for example can enumerate the polyphenylene derivatives of replacement or non-replacement, poly-fluorene derivatives, polyphenylene vinylene derivative, polythiofuran derivative, poly quinoline derivative, poly-triphenylamine derivative, polyvinyl carbazole derivative (polyvinylcarbazole), polyaniline derivative, polyimide derivative, polyamidoimide derivative, polycarbonate derivatives, polyacrylic acid derivative, polystyrene derivative etc.In addition, as conjugation or non-conjugated polymeric thing, can enumerate in the case of necessary and for example to replace with other monomeric unit or the arylidene and/or the heteroarylidene monomeric unit of non-replacement are benzene, biphenyl, terphenyl, naphthalene, anthracene, tetracene, fluorenes, luxuriant and rich with fragrance, pyrene, 1, the 2-benzophenanthrene, pyridine, pyrazine, quinoline, isoquinoline 99.9, acridine, phenanthroline, furans, the pyrroles, thiophene oxazole oxadiazole, thiadiazoles, triazole benzoxazole Ben Bing oxadiazole, diazosulfide, thionaphthene etc., the monomeric unit with triphenylamine skeleton of replacement or non-replacement is a triphenylamine, N-(4-butyl phenyl)-N-diphenylamine, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-[1,1 '-biphenyl]-4,4 '-diamines, N, N '-two (3-tolyl)-N, N '-two (2-naphthyl)-[1,1 '-biphenyl]-4, the polymkeric substance of copolymerization such as 4 '-diamines.
If will be with multipolymer of the present invention or polymer composition active layer material as electroluminescent cell, polymers soln can be coated on the matrix, also can on matrix, reach by the active coating of laminate film shape, wherein can adopt the method for well known to a person skilled in the art, for example ink-jet (inl-jet), casting (cast), dipping, printing or rotary coating (spin coating) etc.In the print process, letterpress, intaglio printing, offset printing (offset) printing, planography, letterpress reverse offset printing (offset) printing, silk screen (screen) printing, photogravure (gravure) printing etc. are arranged.Such laminating method generally can be implemented in-20～+ 300 ℃ of temperature ranges, and 10～100 ℃ be preferred, and 15～50 ℃ be that the spy is good.And, with regard to regard to the drying of stacked polymers soln, generally can implement Air drying, the utilize hot-plate heat drying etc. of (hot plate).
As employed solvent in the solution that contains multipolymer, can use chloroform (chloroform), chloromethane (methylene chloride), ethylene dichloride (dichloroethane), tetrahydrofuran (THF) (tetrahydrofuran), toluene (toluene), dimethylbenzene (xylene), sym-trimethylbenzene (mesitylene), methyl-phenoxide (anisole), acetone (acetone), methyl ethyl ketone (methyl ethyl ketone), ethyl acetate (ethyl acetate), butylacetate (butyl acetate), ethoxyethyl acetate(EA) (ethylcellosolve acetate) etc.
In addition, contain the gross weight of the solution of multipolymer relatively, the high-molecular copolymer that contains the containing metal coordination compound of 0.1～5 weight percent (%) is good, contains 0.2～3 weight % for better.When less than 0.1 weight %, have the tendency that produces film defects such as pin hole, when surpassing 5 weight %, then there is the even tendency of non-uniform film thickness.
The general structure of the electroluminescent cell of the present invention that is made of polymkeric substance of the present invention has been recorded in United States Patent (USP) the 4th, 539, in No. 507 cases and the 5th, 151, No. 629 cases of United States Patent (USP).And, disclose in No. 0443861 case on the books for for example international open WO90/13148 case of the electroluminescent cell that contains polymkeric substance or European patent.
In these electroluminescent cells, normally between at least one electrode is transparent negative electrode (cathod) and anode (anode), contain electroluminescence layer (luminescent layer).And, between electroluminescence layer (luminescent layer) and negative electrode, can insert the electron injecting layer more than one deck and/or the element of electron migration layer, and then between electroluminescence layer (luminescent layer) and anode, can insert hole injection layer and/or hole mobile layer more than one deck.As the material of negative electrode, preferably for example lithium (Li), calcium (Ca), magnesium (Mg), aluminium (Al), indium (In), caesium (Cs), magnesium/aluminium (Mg/Al), lithium fluoride metal or metal alloy such as (LiF).As the anodic material, can be used in other material of being provided with metal (for example gold (Au)) on the transparent base (for example glass or transparent polymer) or having metallic conductivity for example oxide compound (as ITO: material Indium sesquioxide/stannic oxide).
As electronics inject with and/or the electron migration layer, can enumerate contain the oxadiazole derivative is arranged, the layer of materials such as benzoxazole derivative, quinone derivatives, quinoline, quinoxaline derivatives, thiadiazoles derivative, benzothia (oxa) diazol derivatives, triazole derivative, metal-chelating coordination compound.
As hole (hole) inject with and/or the hole mobile layer, can enumerate the layer of materials such as containing copper phthalocyanine (phthalocyanine), triphenylamine derivative, triphenyl methane derivative, Stilbene based compound, hydrazone based compound, carbazole based compound, high molecular arylamine, polyaniline, Polythiophene.
The high-molecular copolymer of containing metal coordination compound of the present invention is suitable as the material as organic EL element.It has good illuminant colour purity and stability especially, and makes film easily, can demonstrate good film and form ability.Therefore, used the organic EL of the present invention of this multipolymer can demonstrate good illuminant colour purity and stability, and productivity is outstanding.
Embodiment
With following embodiment the present invention is described below, but the present invention only is defined in these embodiment.In addition, except embodiment as described below, when using above-mentioned various monomeric unit, the electroluminescent cell that also can obtain having good purity of color, reliability, the characteristics of luminescence.
Synthesizing of embodiment 1 metal complex table 1 (1)
Tetrahydrofuran (THF) (THF with 3-bromo-9-methyl carbazole (30mmol), Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignard reagent).The careful one side that stirs of the Grignard reagent of gained one side under-78 ℃ temperature was splashed into to trimethyl-boron acid esters (trimethylboric acid ester) THF solution (300mmol) inchmeal with time of 2 hours, afterwards in stirring at room 2 days.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of carbazole derivative boric acid (40%) with toluene/acetone (1/2).With the carbazole derivative boric acid (12mmol) that obtains and 1 (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), the result can obtain the clear crystal of carbazole derivative boric acid ester.
In 2-bromopyridine (10mmol), carbazole derivative boric acid ester (10mmol) and Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained 3-(2 '-pyridyl)-9-methyl carbazole solid.
In the three-necked flask of 200ml, insert iridium chloride (III) (1.7mmol), 3-(2 '-pyridyl)-9-methyl carbazole (7.58mmol), ethoxy ethanol 50ml and water 20ml, carry out 30 minutes stirring at room under stream of nitrogen gas, the backflow of carrying out afterwards 24 hours is stirred.Reactant is cooled to room temperature, and throw out to be filtered cleans according to the order of ethanol and acetone after cleaning with water.At room temperature carry out drying under reduced pressure, and obtain two-μ-chloro-four (tetrakis) [3-(2 '-pyridyl)-9-methyl carbazole-N
1', C
2] two iridium (III) pale yellow powder.
In the three-necked flask of 200ml, insert ethoxy ethanol 70ml, two-μ-chloro-four (tetrakis) [3-(2 '-pyridyl)-9-methyl carbazole-N1 ', C
2] two iridium (III) (0.7mmol), the methyl ethyl diketone derivative (2.10mmol) shown in following structural formula and sodium carbonate (9.43mmol), under stream of nitrogen gas, carry out stirring at room, the backflow of carrying out afterwards 15 hours is stirred.
Reactant is cooled off with ice bath, and throw out is filtered washing.By this throw out being carried out silica gel column chromatography (eluant: chloroform/methanol: 30/1) make with extra care, and obtain two [3-(2 '-pyridyl)-9-methyl carbazole-N1 ', C
2] pale yellow powder of (dibromobenzene methyl methyl ethyl diketone (acetylacetonato)) iridium (III).
Synthesizing of embodiment 2 metal complex tables 2 (125)
Tetrahydrofuran (THF) (THF with 2-hydroxyl-6-bromo-9-methyl carbazole (30mmol), Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignard reagent).The careful one side that stirs of the Grignard reagent of gained one side under-78 ℃ temperature was splashed into to trimethyl-boron acid esters (trimethylboric acid ester) THF solution (300mmol) inchmeal with time of 2 hours, afterwards, in stirring at room 2 days.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of carbazole derivative boric acid (40%) with toluene/acetone (1/2).With the carbazole derivative boric acid (12mmol) that obtains and 1 (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), the result can obtain the clear crystal of carbazole derivative boric acid ester.
In 2-bromopyridine (10mmol), carbazole derivative boric acid ester (10mmol) and Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained 2-hydroxyl-6-(2 '-pyridyl)-9-methyl carbazole solid.
In the three-necked flask of 200ml, insert iridium chloride (III) (1.7mmol), 2-hydroxyl-6-(2 '-pyridyl)-9-methyl carbazole (7.58mmol), ethoxy ethanol 50ml and water 20ml, carry out 30 minutes stirring at room under stream of nitrogen gas, the backflow of carrying out afterwards 24 hours is stirred.Reactant is cooled to room temperature, after throw out to be filtered and the washing, cleans according to the order of ethanol and acetone.At room temperature carry out drying under reduced pressure, and obtain two-μ-chloro-four (tetrakis) [2-hydroxyl-6-(2 '-pyridyl)-9-methyl carbazole-N1 ', C
7] pale yellow powder of two iridium (III).
In the three-necked flask of 200ml, insert ethoxy ethanol 70ml, two-μ-chloro-four (tetrakis) [2-hydroxyl-6-(2 '-pyridyl)-9-methyl carbazole-N1 ', C
7] two iridium (III) (0.7mmol), the methyl ethyl diketone derivative (2.10mmol) shown in following structural formula and sodium carbonate (9.43mmol), under stream of nitrogen gas, carry out stirring at room, the backflow of carrying out afterwards 15 hours is stirred.
Reactant is cooled off with ice bath, and throw out is filtered washing.By this this throw out being carried out silica gel column chromatography (eluant: chloroform/methanol: 30/1) make with extra care, thereby obtain two [2-hydroxyl-6-(2 '-pyridyl)-9-methyl carbazole-N
1', C
7] pale yellow powder of (dibromobenzene methyl methyl ethyl diketone (acetylacetonato)) iridium (III).
Synthesizing of embodiment 3 metal complex tables 3 (253)
With 2-bromo-9-Fluorenone (fluorenone) tetrahydrofuran (THF) (THF (30mmol), Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignard reagent).With the Grignard reagent of gained one side under-78 ℃ temperature is careful stir one side and splash into to trimethyl-boron acid esters (trimethylboric acid ester) the THF solution (300mmol) inchmeal with time of 2 hours after, in room temperature, stirred 2.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of fluorenone derivatives boric acid (40%) with toluene/acetone (1/2).With the fluorenone derivatives boric acid (12mmol) that obtains and 1 (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), the result can obtain the clear crystal of fluorenone derivatives boric acid ester.
In 2-bromopyridine (10mmol), fluorenone derivatives boric acid ester (10mmol) and Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained 2-(2 '-pyridyl)-9-Fluorenone solid.
In the three-necked flask of 200ml, insert iridium chloride (III) (1.7mmol), 2-(2 '-pyridyl)-9-Fluorenone (7.58mmol), ethoxy ethanol 50ml and water 20ml, carry out 30 minutes stirring at room under stream of nitrogen gas, the backflow of carrying out afterwards 24 hours is stirred.Reactant is cooled to room temperature, after throw out to be filtered and the washing, cleans according to the order of ethanol and acetone.At room temperature carry out drying under reduced pressure, and obtain two-μ-chloro-four (tetrakis) [2-(2 '-pyridyl)-9-Fluorenone-N
1', C
3] pale yellow powder of two iridium (III).
In the three-necked flask of 200ml, insert ethoxy ethanol 70ml, two-μ-chloro-four (tetrakis) [2-(2 '-pyridyl)-9-Fluorenone-N1 ', C
3] two iridium (III) (0.7mmol), the methyl ethyl diketone derivative (2.10mmol) shown in following structural formula and sodium carbonate (9.43mmol), under stream of nitrogen gas, carry out stirring at room, the backflow of carrying out afterwards 15 hours is stirred.
Reactant is cooled off with ice bath, and throw out is filtered washing.By this throw out being carried out silica gel column chromatography (eluant: chloroform/methanol: 30/1) make with extra care, thereby obtained two [2-(2 '-pyridyl)-9-Fluorenone-N1 ', C
3] pale yellow powder of (dibromobenzene methyl methyl ethyl diketone (acetylacetonato)) iridium (III).
Synthesizing of example I-4 quinoline hypoboric acid ester (I-Q-1)
With 6,6 '-two [2-(4-bromophenyl)-3,4-phenylbenzene quinoline] (30mmol) tetrahydrofuran (THF) (THF, Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignardreagent).With the Grignard reagent of gained one side under-78 ℃ temperature is careful stir one side and splash into to trimethyl-boron acid esters (trimethylboric acid ester) the THF solution (300mmol) inchmeal with time of 2 hours after, in room temperature, stirred 2.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of quinoline hypoboric acid (40%) with toluene/acetone (1/2).The quinoline hypoboric acid (12mmol) and 1 that obtains, 2-ethylene glycol (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), and the result can obtain the clear crystal (83%) of quinoline hypoboric acid ester.
Synthesizing of the high-molecular copolymer (I-P-1) of example I-5 containing metal coordination compound
In synthetic metal complex (1) among the embodiment 1 (1mmol), in the dibromo two benzene oxadiazoles (9mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example I-4 synthetic quinoline hypoboric acid ester (I-Q-1) (5mmol) with Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (I-P-1) of containing metal coordination compound.
In addition, the compound that obtains is confirmed with NMR spectrum, IR spectrum.To compound shown below also is like this.
Synthesizing of the high-molecular copolymer (I-P-2) of example I-6 containing metal coordination compound
In synthetic metal complex (125) among the embodiment 2 (1mmol), in the dibromo two benzene oxadiazoles (9mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example I-4 synthetic quinoline hypoboric acid ester (I-Q-1) (5mmol) with Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid of leaching in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' s extractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (I-P-2) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (I-P-3) of example I-7 containing metal coordination compound
In 3 synthetic metal complexes of embodiment (253) (1mmol), synthetic quinoline hypoboric acid ester (I-Q-1 (5mmol) and Pd (0) (PPh in the dibromo two benzene oxadiazoles (9mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example I-4
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (I-P-3) of containing metal coordination compound.
The making (I-1) of example I-8 organic EL
The toluene solution of the high-molecular copolymer (I-P-1) of the containing metal coordination compound that will in example I-5, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum-evaporator, and the order with calcium (Ca) (thickness 20nm), Al (thickness 100nm) on above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=450nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (I-2) of example I-9 organic EL
The toluene solution of the high-molecular copolymer (I-P-2) of the containing metal coordination compound that will in example I-6, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum-evaporator, and the order with lithium fluoride (LiF) (thickness 0.5nm), Al (thickness 100nm) on the above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and LiF/Al is that negative electrode has applied voltage, and the result has observed the orange-colored light sent (wavelength X=590nm) under about 5V (volt).This orange light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (I-3) of example I-10 organic EL
Except the high-molecular copolymer (I-P-3) with the containing metal coordination compound replaced the high-molecular copolymer (I-P-1) of containing metal coordination compound, other used the mode identical with example I-8 to make ITO/ polymer light-emitting layer/Ca/Al element.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=450nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
Comparative example 1
Except replace the high-molecular copolymer (I-P-1) of containing metal coordination compound in order to the poly quinoline shown in the following structural formula, other uses the mode identical with example I-8 to make ITO/ polymer light-emitting layer/Ca/Al element.With resulting ITO/ polymer light-emitting layer/the Ca/Al element is connected to power supply, is anode with ITO, Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=430nm) under about 10V (volt).Its luminous color can pass in time become by blueness light blue.
Comparative example 2
Except using the represented dioctyl fluorene of following structural formula (dioctylfluorene)/benzothiazole (benzothiazole) multipolymer to replace the high-molecular copolymer (I-P-1) of containing metal coordination compound, produce ITO/ polymer light-emitting layer/LiF/Al element with the method identical with example I-8.With resulting ITO/ polymer light-emitting layer/the LiF/Al element is connected to power supply, is anode with ITO, LiF/Al is that negative electrode has applied voltage, and the result has observed the sodium yellow that sends (λ=548nm) under about 8V.Its luminous color can passing in time become yellow-white by yellow.
Comparative example 3
10
-5In the vacuum reaction chamber of Pa (chamber),, ITO (tin indium oxide) is being patterned on 2 millimeters (mm) wide glass substrate, is forming d-NPD film as hole transporting layer with the thickness of 40nm by utilizing the vacuum vapour deposition of resistive heating.Above it, with the metal complex Ir (ppy) of structure as follows
3Carried out common evaporation with CBP, the weight ratio of metal complex is 5%.
And then, as the electron supplying layer evaporation the thick above-mentioned Alq of 30nm
3Thereon as the negative electrode layer evaporation LiF 0.5～2nm, Al 100～150nm.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.The element that obtains is connected in power supply, is anode with ITO, and LiF/Al is that negative electrode has applied voltage, and the result has observed the green light sent (wavelength X=516nm) under about 6V (volt).Measured at certain electric current (50mA/cm
2) briliancy time of reducing by half when driving down is 100 hours.
Synthesizing of example II-4 quinoline hypoboric acid ester (II-Q-1)
With 6,6 '-two [2-(4-bromophenyl)-3,4-phenylbenzene quinoline] (30mmol) tetrahydrofuran (THF) (THF, Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignardreagent).With the Grignard reagent of gained one side under-78 ℃ temperature is careful stir one side and splash into to trimethyl-boron acid esters (trimethylboric acid ester) the THF solution (300mmol) inchmeal with time of 2 hours after, in room temperature, stirred 2.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of quinoline hypoboric acid (40%) with toluene/acetone (1/2).With the quinoline hypoboric acid (12mmol) and 1 that obtains, 2-ethylene glycol (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), and the result can obtain the clear crystal (83%) of quinoline hypoboric acid ester.
Synthesizing of the high-molecular copolymer (II-P-1) of example II-5 containing metal coordination compound
In 1 synthetic metal complex of embodiment (1) (1mmol), synthetic quinoline hypoboric acid ester (II-Q-1) (5mmol) in the dibromo two benzene oxadiazoles (8mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example II-4, tribromo branched structure monomer (1mmol) and Pd (0) be (PPh3) in the toluene solution of 4 (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (II-P-1) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (II-P-2) of example II-6 containing metal coordination compound
In 2 synthetic metal complexes of embodiment (125) (1mmol), in the dibromo two benzene oxadiazoles (8.5mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example II-4 synthetic quinoline hypoboric acid ester (II-Q-1) (5mmol), tribromo branched structure monomer (0.5mmol) and Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (II-P-2) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (II-P-3) of example II-7 containing metal coordination compound
In 3 synthetic metal complexes of embodiment (253) (1mmol), in the dibromo two benzene oxadiazoles (8mmol) shown in following structural formula, two cyclohexyloxy dibromobenzenes (5mmol), example II-4 synthetic quinoline hypoboric acid ester (II-Q-1) (5mmol), tribromo branched structure monomer (1mmol) and Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (II-P-3) of containing metal coordination compound.
The making (II-1) of example II-8 organic EL
The toluene solution of the high-molecular copolymer (II-P-1) of the containing metal coordination compound that will in example II-5, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with calcium (Ca) (thickness 20nm), Al (thickness 100nm) on the above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=440nm) at about 4.5V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (II-2) of example II-9 organic EL
The toluene solution of the high-molecular copolymer (II-P-2) of the containing metal coordination compound that will in example II-6, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with lithium fluoride (LiF) (thickness 0.5nm), Al (thickness 100nm) on the above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and LiF/Al is that negative electrode has applied voltage, and the result has observed the orange-colored light sent (wavelength X=570nm) at about 5.5V (volt).This orange light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (II-3) of example II-10 organic EL
Except the high-molecular copolymer (II-P-3) with the containing metal coordination compound replaced the high-molecular copolymer (II-P-1) of containing metal coordination compound, other used the mode identical with example II-8 to make ITO/ polymer light-emitting layer/Ca/Al element.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=447nm) under about 4.5V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
Synthesizing of EXAMPLE III-4 two cyclohexyloxy benzene hypoboric acid ester (III-PP-1)
With 2,5-two bromo-1, tetrahydrofuran (THF) (the THF of 4-two hexyloxy benzene (30mmol), Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignardreagent).With the Grignard reagent of gained one side under-78 ℃ temperature is careful stir one side and splash into to trimethyl-boron acid esters (trimethylboric acid ester) the THF solution (300mmol) inchmeal with time of 2 hours after, in room temperature, stirred 2.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of two cyclohexyloxy benzene hypoboric acid (50%) with toluene/acetone (1/2).The two cyclohexyloxy benzene hypoboric acid (12mmol) and 1 that obtain, 2-ethylene glycol (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), and the result can obtain the clear crystal (80%) of two cyclohexyloxy benzene hypoboric acid esters.
Synthesizing of the high-molecular copolymer (III-P-1) of EXAMPLE III-5 containing metal coordination compound
In 1 synthetic metal complex of embodiment (1) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, synthetic two cyclohexyloxy benzene hypoboric acid esters (10mmol) in 3,4] oxadiazoles (9mmol), the EXAMPLE III-4, with Pd (0) (PPh
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (III-P-1) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (III-P-2) of EXAMPLE III-6 containing metal coordination compound
In 2 synthetic metal complexes of embodiment (125) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, 3,4] oxadiazoles (4mmol), 2-(2, the 5-dibromo phenyl)-[synthetic two cyclohexyloxy benzene hypoboric acid esters (10mmol) and Pd (0) are (PPh3) in the toluene solution of 4 (0.2mmol) in 1,3,4] oxadiazoles (4mmol), the EXAMPLE III-4 for the 5-phenyl, under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
2-(2，5-Dibromo-phenyl)-5-phenyl-[1，3，4]oxadiazole、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (III-P-2) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (III-P-3) of EXAMPLE III-7 containing metal coordination compound
In 3 synthetic metal complexes of embodiment (253) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, 3,4] oxadiazoles (9mmol), 9,9-two hot fluorenes-2, synthetic two cyclohexyloxy benzene hypoboric acid esters (5mmol) and Pd (0) (PPh in 7-hypoboric acid ester (5mmol), the EXAMPLE III-4
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
9，9-Dioctyffluorene-2，7-bis(pinacol?boronate)、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (III-P-3) of containing metal coordination compound.
The making (III-1) of EXAMPLE III-8 organic EL
The toluene solution of the high-molecular copolymer (III-P-1) of the containing metal coordination compound that will in EXAMPLE III-5, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with calcium (Ca) (thickness 20nm), Al (thickness 100nm) on the above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=455nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (III-2) of EXAMPLE III-9 organic EL
The toluene solution of the high-molecular copolymer (III-P-2) of the containing metal coordination compound that will in EXAMPLE III-6, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with lithium fluoride (LiF) (thickness 0.5nm), Al (thickness 100nm) on the above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and LiF/Al is that negative electrode has applied voltage, and the result has observed the orange-colored light sent (wavelength X=588nm) under about 5V (volt).This orange light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (III-3) of EXAMPLE III-10 organic EL
Except the high-molecular copolymer (III-P-3) with the containing metal coordination compound replaced the high-molecular copolymer (III-P-1) of containing metal coordination compound, other used the mode identical with EXAMPLE III-8 to make ITO/ polymer light-emitting layer/Ca/Al element.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=460nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
Comparative example 4
Except replace the high-molecular copolymer (III-P-1) of containing metal coordination compound with poly-two hot fluorenes, other uses the mode identical with EXAMPLE III-8 to make ITO/ polymer light-emitting layer/Ca/Al element.With resulting ITO/ polymer light-emitting layer/the Ca/Al element is connected to power supply, is anode with ITO, Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=430nm) under about 6V (volt).Its luminous color can passing in time become yellow-green colour by blueness.
Synthesizing of EXAMPLE IV-4 two cyclohexyloxy benzene hypoboric acid ester (IV-PP-1)
With 2,5-two bromo-1, tetrahydrofuran (THF) (the THF of 4-two hexyloxy benzene (30mmol), Tetrahydrofuran) solution, under argon stream, one side is careful to be stirred in the THF mixture that simultaneously makes an addition to magnesium (1.9 gram (g), 80 mmoles (mmol)) slowly, is prepared into Grignard reagent (grignardreagent).With the Grignard reagent of gained one side under-78 ℃ temperature is careful stir one side and splash into to trimethyl-boron acid esters (trimethylboric acid ester) the THF solution (300mmol) inchmeal with time of 2 hours after, in room temperature, stirred 2.The reaction mixture injection is contained 5% finely divided ice dilute sulphuric acid and stirring.Extract the resulting aqueous solution with toluene, and after extract concentrated, can obtain colourless solid.By making resulting solid carry out recrystallize, can obtain the clear crystal of two cyclohexyloxy benzene hypoboric acid (50%) with toluene/acetone (1/2).With the two cyclohexyloxy benzene hypoboric acid (12mmol) and 1 that obtain, 2-ethylene glycol (1,2-ethanediol) (30mmol) in reflux in toluene after 10 hours, recrystallize from toluene/acetone (1/4), and the result can obtain the clear crystal (80%) of two cyclohexyloxy benzene hypoboric acid esters.
Synthesizing of the high-molecular copolymer (IV-P-1) of EXAMPLE IV-5 containing metal coordination compound
In 1 synthetic metal complex of embodiment (1) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, synthetic two cyclohexyloxy benzene hypoboric acid esters (10mmol), tribromo branched structure monomer (1mmol) and Pd (0) (PPh in 3,4] oxadiazoles (8mmol), the EXAMPLE IV-4
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (IV-P-1) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (IV-P-2) of EXAMPLE IV-6 containing metal coordination compound
In 2 synthetic metal complexes of embodiment (125) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, 3,4] oxadiazoles (3.5mmol), 2-(2, the 5-dibromo phenyl)-5-phenyl [1, synthetic two cyclohexyloxy benzene hypoboric acid esters (10mmol), tribromo branched structure monomer (0.5nmol) and Pd (0) (PPh in 3,4] oxadiazoles (4mmol), the EXAMPLE IV-4
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
2-(2，5-Dibromo-phenyl)-5-phenyl-[1，3，4]oxadiazole、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (IV-P-2) of containing metal coordination compound.
Synthesizing of the high-molecular copolymer (IV-P-3) of example II-7 containing metal coordination compound
In 3 synthetic metal complexes of embodiment (253) (1mmol), shown in following structural formula 2, two (the 4-bromophenyls) [1 of 5-, 3,4] oxadiazoles (8mmol), 9,9-two hot fluorenes-2, synthetic two cyclohexyloxy benzene hypoboric acid esters (5mmol), monomer (1mmol) and Pd (0) (PPh in 7-hypoboric acid ester (5mmol), the EXAMPLE IV-4 with tetrabromo branched structure
3)
4In the toluene solution (0.2mmol), under argon stream, with the salt of wormwood (K of 2M
2CO
3) aqueous solution adding, one side stirs intensely, and one side is carried out 48 hours backflow.
2，5-Bis-(4-bromo-phenyl)-[1，3，4]oxadiazole、
9，9-Dioctylfluorene-2，7-bis(pinacol?boronate)、
2-(4-[1，3，2]Dioxaborolan-2-yl-2，5-dicyclohexyloxy-phenyl)-[1，3，2]dioxaborolane
After reaction mixture is cooled to room temperature, flow in a large amount of methyl alcohol, make solid precipitation.With the solid suction filtration of separating out and with methanol cleaning, obtained solid.After being dissolved in the solid that filters taking-up in the toluene, be injected in a large amount of acetone, make solid precipitation.Clean with the solid suction filtration of separating out and with acetone, obtained solid.Then, repeating twice above-mentioned redeposition of acetone that utilizes handles.Afterwards, be dissolved in the solid that obtains in the toluene after, add cationic anionic exchange resin (Japanese Ao Jianuo system ion exchange resin), stirs after 1 hour, through suction filtration recovery polymers soln.Then, repeat the above-mentioned TREATMENT OF ION EXCHANGE RESINS of utilizing twice.The polymers soln that reclaims is injected a large amount of methyl alcohol, make solid precipitation.Then, in soxhlet's extractor (Soxhlet ' sextractor), utilize acetone extract to clean 24 hours the solid that obtains, obtain the high-molecular copolymer (IV-P-3) of containing metal coordination compound.
The making (IV-1) of EXAMPLE IV-8 organic EL
The toluene solution of the high-molecular copolymer (IV-P-1) of the containing metal coordination compound that will in EXAMPLE IV-5, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with calcium (Ca) (thickness 20nm), Al (thickness 100nm) on above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=445nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (IV-2) of EXAMPLE IV-9 organic EL
The toluene solution of the high-molecular copolymer (IV-P-2) of the containing metal coordination compound that will in EXAMPLE IV-6, obtain (1.0 weight percents (wt%)), under the exsiccant nitrogen environment, be coated on spin-coating method ITO (tin indium oxide) is patterned on 2 millimeters (mm) wide glass substrate, formed polymer light-emitting layer (thickness 70nm).Then, under the exsiccant nitrogen environment, on hot-plate 80 ℃ of heat dryings 5 minutes.The glass substrate that obtains is moved on in the vacuum evaporation device, and the order with lithium fluoride (LiF) (thickness 0.5nm), Al (thickness 100nm) on above-mentioned luminescent layer has formed electrode.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and LiF/Al is that negative electrode has applied voltage, and the result has observed the orange-colored light sent (wavelength X=580nm) under about 5V (volt).This orange light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
The making (IV-3) of EXAMPLE IV-10 organic EL
Except the high-molecular copolymer (IV-P-3) with the containing metal coordination compound replaced the high-molecular copolymer (IV-P-1) of containing metal coordination compound, other used the mode identical with EXAMPLE IV-8 to make ITO/ polymer light-emitting layer/Ca/Al element.When measuring the characteristic of organic EL, at room temperature, utilize the small electric flowmeter 4140B of ヒ ユ one レ Star ト パ Star カ one De corporate system to measure current-voltage characteristic, utilize the SR-3 of ト プ コ Application corporate system to measure glorious degrees.With ITO is anode, and Ca/Al is that negative electrode has applied voltage, and the result has observed the blue light that sends (wavelength X=455nm) under about 4V (volt).This blue light through after 500 hours, the variation on its tone do not occur yet in 25 ℃.
Claims (10)
1. high-molecular copolymer that contains metal complex, wherein contain any metal complex monomeric unit with following formula (1)～(12) expression, with be selected from replace or the conjugative monomer unit of the branched structure monomeric unit of the arylidene of quinoline monomeric unit, replacement or the non-replacement of non-replacement and/or heteroarylidene monomeric unit, replacement or non-replacement and replacement or non-replacement in one or more monomeric unit
B：＞O，＞S，＞C＝O，＞SO
2，＞CR
2
In the formula, M is iridium, rhodium, ruthenium, osmium, palladium or platinum; N is 1 or 2; Ring A is the ring compound that contains with M bonded nitrogen-atoms; X
1～X
7And R represents respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5,-SiR
6R
7R
8And-NR
9R
10Substituting group, R wherein
1～R
10The expression hydrogen atom, halogen atom, cyano group, nitro, carbon number is 1～22 a straight chain, part or all halogen-substituted alkyl that is replaced by halogen atom of hydrogen atom on ring-type or branched-chain alkyl or these bases, carbon number is 6～30 a aryl, carbon number is aralkyl or the part of the hydrogen atom on these bases or the halogen substituted aryl that is all replaced by halogen atom that 2～30 heteroaryl or carbon number are 7～30, the halogen substituted heteroaryl, the halogen substituted aralkyl; R
1～R
10Can be separately identical, also can be difference, X
1～X
7Can be separately identical, also can be difference; Ring A can have and use X
1-X
7The identical substituting group of group of definition; Ring C is incorporated into M and in conjunction with basic bonded compound; Ring C can have and use X
1-X
7The identical substituting group of group of definition,
The branched structure monomeric unit of described replacement or non-replacement is the unit that is selected from structure shown below,
In the formula, a plurality of Y represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8The expression carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but is the substituting group of the position of substitution that is incorporated into the phenyl ring of branched structure skeleton; And p is the integer of expression 0～4,
The conjugative monomer unit of described replacement or non-replacement is the unit shown in the formula (13-2),
In the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but V is the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue, R
1, R
2Be with carbon-carbon double bond in carbon atom bonded substituting group; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously.
2. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein this high-molecular copolymer that contains metal complex contains the quinoline monomeric unit of replacement shown in any metal complex monomeric unit shown in above-mentioned formula (1)～(12), the formula (13-1) or non-replacement and the arylidene and/or the heteroarylidene monomeric unit of replacement or non-replacement
Perhaps
In the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but is the substituting group that is incorporated into the position of substitution in the quinoline residue; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene; E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-)
m-O-combines base with the divalent of-Q-, wherein m is 1～3 integer, W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, Ar ' is an arylidene, Ra ' is expressed as the base that is selected from alkylidene group, arylidene and alkylidene group/arylidene mixed base separately respectively, Het ' is a heteroarylidene, Q is the divalent base that contains level Four carbon,
And have structure with formula (14) expression in conjunction with the base of this monomeric unit respectively,
-(G)b- (14)
In the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents that carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer.
3. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein this high-molecular copolymer that contains metal complex contains any represented metal complex monomeric unit of above-mentioned formula (1)～(12), the replacement shown in the formula (13-1) or the quinoline monomeric unit of non-replacement and the branched structure monomeric unit of replacement or non-replacement
In the formula, a plurality of V represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8The expression carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and that these substituting groups can be separately is identical, also can be difference, but is the substituting group that is incorporated into the position of substitution in the quinoline residue; And a represents 0～3 integer separately respectively; D is the base that is selected from singly-bound and arylidene; E be selected from singly-bound ,-O-,-S-,-C (O)-,-S (O)-,-S (O
2)-,-W-,-(O-W-)
m-O-combines base with the divalent of-Q-, wherein m is 1～3 integer, W be selected from-Ra-,-Ar '-,-Ra-Ar '-,-Ra '-O-Ra '-,-Ra '-C (O) O-Ra '-,-Ra '-NHCO-Ra '-,-Ra-C (O)-Ra-,-Ar '-C (O)-Ar '-,-Het '-,-Ar '-S-Ar '-,-Ar '-S (O)-Ar '-,-Ar '-S (O
2)-Ar '-with-Ar '-Q-Ar '-the divalent base, wherein Ra is an alkylidene group, Ar ' is an arylidene, Ra ' is expressed as the base that is selected from alkylidene group, arylidene and alkylidene group/arylidene mixed base separately respectively, Het ' is a heteroarylidene, Q is the divalent base that contains level Four carbon,
And have structure with formula (14) expression in conjunction with the base of this monomeric unit respectively,
-(G)b- (14)
In the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-the divalent base, wherein R represents that carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer,
The branched structure monomeric unit of described replacement or non-replacement is the unit that is selected from structure shown below,
In the formula, a plurality of Y represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8The expression carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but is the substituting group of the position of substitution that is incorporated into the phenyl ring of branched structure skeleton; And p is the integer of expression 0～4.
4. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein this high-molecular copolymer that contains metal complex contains the replacement shown in any metal complex monomeric unit shown in above-mentioned formula (1)～(12), the formula (13-2) or the conjugative monomer unit of non-replacement
In the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but V is the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue, R
1, R
2Be with carbon-carbon double bond in carbon atom bonded substituting group; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously,
And have structure with formula (14) expression in conjunction with the base of this monomeric unit respectively,
-(G)b- (14)
In the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein, R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer.
5. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein this high-molecular copolymer that contains metal complex contains the conjugative monomer unit of replacement shown in any metal complex monomeric unit shown in above-mentioned formula (1)～(12), the formula (13-2) or non-replacement and the branched structure monomeric unit of replacement or non-replacement
In the formula, Ar
1With Ar
2The arylidene and/or the heteroarylidene of expression divalent; A plurality of V, R
1, R
2Expression is selected from-R respectively separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8Represent respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but V is the substituting group that is incorporated into the position of substitution in arylidene or the heteroarylidene residue, R
1, R
2Be with carbon-carbon double bond in carbon atom bonded substituting group; And a and b represent the integer more than 0 or 0 separately respectively; R
1With R
2Can represent hydrogen atom separately respectively; N, m, l represent 0 or 1 separately respectively; N, m, l are not 0 simultaneously,
And, have structure with formula (14) expression in conjunction with the base of this monomeric unit respectively,
-(G)b- (14)
In the formula, G for be selected from-O-,-R-O-R-,-S-,-NR-,-CR
2-,-SiR
2-,-SiR
2-O-SiR
2-and-SiR
2-O-SiR
2-O-SiR
2-divalent radical, wherein R represents respectively that separately carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, and b is 0～1 integer,
The branched structure monomeric unit of described replacement or non-replacement is the unit that is selected from structure shown below,
In the formula, a plurality of Y represent respectively to be selected from-R separately
1,-OR
2,-SR
3,-OCOR
4,-COOR
5With-SiR
6R
7R
8Substituting group, R wherein
1～R
8The expression carbonatoms is the alkyl of 1～22 straight chain, ring-type or side chain, or carbonatoms is 2～30 aryl or heteroaryl, that these substituting groups can be separately is identical, also can be difference, but is the substituting group of the position of substitution that is incorporated into the phenyl ring of branched structure skeleton; And p is the integer of expression 0～4.
6. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein in above-mentioned formula (1)～(12), this ring A is for having and using X
1-X
7Identical substituent pyridine, quinoline, benzoxazole, benzothiazole, benzoglyoxaline, benzotriazole, imidazoles, pyrazoles, oxazole, thiazole, triazole, benzopyrazoles, triazine or the isoquinoline 99.9 of group of definition.
7. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein in above-mentioned formula (1)～(12), X
1～X
7The definition and the X that perhaps encircle A and had
1～X
7At least 1 in the identical substituting group is fluorine atom or trifluoromethyl.
8. the high-molecular copolymer that contains metal complex as claimed in claim 1, wherein in above-mentioned formula (1)～(12), M is an iridium.
9. polymer composition, this polymer composition is that the hybrid right requirement 1 described high-molecular copolymer that contains metal complex forms in conjugation or unconjugated polymkeric substance.
10. organic electroluminescent device, this organic electroluminescent device are to utilize described high-molecular copolymer or the described polymer composition of claim 9 that contains metal complex of claim 1 to make.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP173799/2003 | 2003-06-18 | ||
| JP173933/2003 | 2003-06-18 | ||
| JP2003173799 | 2003-06-18 | ||
| JP173986/2003 | 2003-06-18 | ||
| JP173874/2003 | 2003-06-18 |
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|---|---|
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| CN100591708C true CN100591708C (en) | 2010-02-24 |
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| CN111874900B (en) * | 2020-07-20 | 2022-12-23 | 河南大学 | A kind of metal coordination block copolymer, its preparation method and application |
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