CN113583056B - Light-emitting material of 6/5/6 four-tooth ring metal platinum or palladium complex based on spirofluorene-spirofluorene structure and application thereof - Google Patents
Light-emitting material of 6/5/6 four-tooth ring metal platinum or palladium complex based on spirofluorene-spirofluorene structure and application thereof Download PDFInfo
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- CN113583056B CN113583056B CN202111011862.0A CN202111011862A CN113583056B CN 113583056 B CN113583056 B CN 113583056B CN 202111011862 A CN202111011862 A CN 202111011862A CN 113583056 B CN113583056 B CN 113583056B
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- 239000000463 material Substances 0.000 title claims abstract description 72
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052763 palladium Inorganic materials 0.000 title abstract description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004305 biphenyl Substances 0.000 claims abstract description 10
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 abstract description 25
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 abstract description 19
- 101150091653 PYD2 gene Proteins 0.000 abstract description 5
- 238000005401 electroluminescence Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000859 sublimation Methods 0.000 abstract description 2
- 230000008022 sublimation Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000010410 layer Substances 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 239000002904 solvent Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 15
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
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- 238000000295 emission spectrum Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 238000003775 Density Functional Theory Methods 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
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- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- -1 hydroxy, mercapto Chemical class 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
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- 150000001875 compounds Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 230000005281 excited state Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- CUQGKGMUSQKHFO-UHFFFAOYSA-N 9-(6-carbazol-9-ylpyridin-2-yl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=N1 CUQGKGMUSQKHFO-UHFFFAOYSA-N 0.000 description 2
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- OPPSYCGZHQVDPM-UHFFFAOYSA-N 2-bromo-4-tert-butyl-1-(4-tert-butylphenyl)benzene Chemical group C1=CC(C(C)(C)C)=CC=C1C1=CC=C(C(C)(C)C)C=C1Br OPPSYCGZHQVDPM-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a luminescent material based on a spirofluorene-spirofluorene structure 6/5/6 four-tooth ring metal platinum or palladium complex and application thereof. The four-tooth ring metal platinum (II) or palladium (II) complex has a structure shown in the following general formula, and the four-tooth ring metal platinum (II) or palladium (II) complex links the spirofluorene ring through a biphenyl structure and a derivative thereof, so that a rigid complex structure which is only linked through carbon atoms is constructed, and the stability of molecules in photoluminescence and electroluminescence is improved. The complex Pt (bp-1) is not decomposed in sublimation and purification, and the green OLED device prepared by doping the complex Pt (bp-1) has peak brightness reaching 16644 cd/m 2 when PYD2 is taken as a main body material, so that the complex Pt (bp-1) has wide application prospect in the fields of OLED display, illumination and the like.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a luminescent material of a 6/5/6 four-tooth ring metal platinum (II) or palladium (II) complex with a spirofluorene-spirofluorene structure, which can be used in the fields of OLED display and illumination.
Background
Organic light emitting devices or diodes (OLEDs) are devices that utilize light emitting organic semiconductors to convert electrical energy into light energy through Electroluminescence (EL), with great potential in developing new generation flat panel displays and energy-efficient solid state light sources. The OLED display technology has the following advantages over Liquid Crystal Display (LCD) display: self-luminescence, flexibility, high response speed, transparent display, low driving voltage, high luminous efficiency and resolution, high contrast, wide viewing angle and the like. The technology has become a new generation of full-color display and illumination technology, and has wide and huge application prospect in the fields of electronic products such as mobile phones, computers, televisions, flexible and foldable screens and the like.
Obviously, the light-emitting material is the most critical material element among the organic electroluminescent elements. However, currently available luminescent materials have a number of disadvantages, including less than ideal color purity and lifetime. If the color purity is low, the brightness and luminous efficiency of the display screen are greatly reduced when the color purity is applied to the display screen. In recent years, research on tetradentate platinum (II) complexes has fully demonstrated that tetradentate structure backbones are beneficial to improving molecular rigidity, thereby reducing non-radiative decay due to molecular deformation. The biphenyl bridging ligand is introduced into the tetradentate platinum (II) complex, and all bridging atoms adopt carbon atoms, so that the rigidity of the molecule is further improved, the rotation and vibration of the ligand molecule can be effectively inhibited, the deformation of the molecular structure is minimized, the non-radiative transition of an excited state is reduced, and the improvement of the emission quantum efficiency and the luminous color purity is facilitated. In addition, spirofluorene biphenyl groups and derivatives thereof are introduced on the ligand, and such large substituent groups are connected to the coordinated framework, so that excimer formation is prevented, triplet-triplet quenching caused by intermolecular interaction can be reduced, and the emission quantum efficiency is improved.
Although the development of metal organic small molecule phosphorescent materials has been greatly advanced at present, the metal organic small molecules capable of meeting the commercialization demands are limited so far, and therefore, the development of new luminescent materials still has important significance.
Disclosure of Invention
The embodiment of the invention provides a 6/5/6 four-tooth ring metal platinum (II) or palladium (II) complex based on a spirofluorene-spirofluorene structure, which is characterized in that the four-tooth ring metal platinum (II) or palladium (II) complex phosphorescence luminescent material has a structure shown in a general formula (I):
Wherein:
the metal M is Pd or Pt;
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13 And Y 14 each independently represents CH or N;
R 1、R2、R3、R4、R5、R6、R7 and R 8 each independently represent a mono-, di-, tri-, tetra-, or unsubstituted substituent, and R 1、R2、R3、R4、R5、R6、R7 and R 8 are each independently hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or di-alkylamino, mono-or di-arylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoryl, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric groups, or combinations thereof; and two or more adjacent R 1、R2、R3、R4、R5、R6、R7 and R 8 are each independently or selectively joined to form a fused ring.
The 6/5/6 four-tooth ring metal platinum (II) or palladium (II) complex based on a spirofluorene-spirofluorene structure, optionally, the platinum (II) or palladium (II) complex has one of the following structures:
Wherein, the metal M is Pd or Pt,
The above-mentioned 6/5/6 four-tooth ring metal platinum (II) or palladium (II) complex based on a spirofluorene-spirofluorene structure provided by the embodiment of the present invention has a spirofluorene-spirofluorenyl stable structure based on biphenyl and its derivative linkage, and the photophysical properties of the complex are regulated by regulating the structure and position of substituents on the ligand.
Further, the tetradentate 6/5/6 cyclometalated platinum (II) or palladium (II) complex is characterized in that the platinum (II) or palladium (II) complex has a spirofluorene-spirofluorene structure based on biphenyl and its derivative linkage, and the linking atoms at both sides of the ligand are only carbon atoms.
Further, the four-tooth ring metal platinum (II) or palladium (II) complex is used as an electroluminescent material or a photoluminescent material.
Further, the device comprises a metal platinum (II) or palladium (II) complex of a spirofluorene-spirofluorene structural unit.
Further, the device is characterized in that the device is a full color display, a photovoltaic device, a light emitting display device, or an organic light emitting diode.
Further, the device is characterized by comprising at least one cathode, at least one anode and at least one light-emitting layer, wherein at least one of the light-emitting layers comprises any one of the metal platinum (II) or palladium (II) complexes containing spirofluorene-spirofluorene structural units.
Further, the device is characterized in that the device is an organic light emitting diode, and the light emitting layer of the device contains the metal platinum (II) or palladium (II) complex containing a spirofluorene-spirofluorene structural unit and a corresponding host material, wherein the mass percentage of the metal platinum (II) or palladium (II) complex is 1-50%, and the host material is not limited.
Further, a display or lighting device, characterized in that said display or lighting device comprises said device.
The invention aims to provide a 6/5/6 four-tooth ring metal platinum (II) or palladium (II) complex containing a spirofluorene-spirofluorene structure, which links spirofluorene rings through a biphenyl structure and derivatives thereof to construct a rigid complex structure only linked through carbon atoms, thereby being beneficial to the stability of molecules in photoluminescence and electroluminescence. By structural modification, for example, tert-butyl is introduced into a ligand structure, the substituent structure has the functions of regulating electron distribution and increasing molecular solubility, and is also beneficial to the film forming property of material molecules and the improvement of the photophysical properties of the material molecules. Furthermore, such platinum (II) or palladium (II) complexes provide a new approach for the development of luminescent materials.
Drawings
FIG. 1 is a graph of the emission spectrum of Pt (bp-1) in methylene chloride solution at room temperature, where RT represents room temperature and DCM is methylene chloride, under an embodiment.
FIG. 2 is a graph of the emission spectrum of Pt (bp-2) in methylene chloride solution at room temperature, where RT represents room temperature and DCM is methylene chloride, under an embodiment.
FIG. 3 is a graph of the emission spectrum of Pt (bp-1-t) in a dichloromethane solution at room temperature, where RT represents room temperature and DCM is dichloromethane, under an embodiment.
FIG. 4 is a comparison of emission spectra of Pt (bp-1), pt (bp-2), and Pt (bp-1-t) in dichloromethane at room temperature in an embodiment, where RT represents room temperature and DCM is dichloromethane.
FIG. 5-1 is a distribution of HOMO and LUMO orbitals of Pt (bp-1), pt-3, pt-4, pt-5, pt-6 calculated by Density Functional Theory (DFT), where gap represents the energy level difference between HOMO and LUMO.
FIG. 5-2 shows the HOMO and LUMO orbital distributions of Pt (bp-1-t), pt (bp-2), pt-7, pt-8 calculated by Density Functional Theory (DFT).
FIGS. 5-3 are HOMO and LUMO orbital distributions of Pt-9, pt (bp-1) 0, pt (bp-1) 1, pt (bp-1) 2 calculated by Density Functional Theory (DFT).
FIG. 6 is a schematic structural diagram of an organic light emitting device prepared by using Pt (bp-1) as a doping material.
FIG. 7 is an electroluminescent spectrum of an OLED device employing 10% complex Pt (bp-1) doped, wherein mCBP represents the host material 4,4' -bis (9-carbazolyl) biphenyl and PYD2 represents the host material 2, 6-bis (9-carbazolyl) pyridine.
FIG. 8 is a current density-voltage-luminance curve for an OLED device employing 10% complex Pt (bp-1) doped, wherein mCBP represents the host material 4,4' -bis (9-carbazolyl) biphenyl and PYD2 represents the host material 2, 6-bis (9-carbazolyl) pyridine.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive.
Detailed Description
The present disclosure may be understood more readily by reference to the following detailed description and the examples included therein.
The following examples, which are merely exemplary of the present disclosure and do not limit the scope of the claims, provide one of ordinary skill in the art with a means of making and evaluating the compounds described herein and their OLED devices. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise indicated, temperature is in units of degrees celsius or at ambient temperature and pressure is at or near atmospheric pressure.
The examples provided below with respect to the synthesis, composition, article, device or method of compounds are merely intended to provide a general method to the industry, but the preparation of such compounds is not limited to this method. In this technical field, since the compounds protected in this patent are easy to modify and prepare, the preparation thereof can be carried out by the methods listed below or by other methods. The following examples are given by way of example only and are not intended to limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants, and reaction process may all be varied to prepare the compounds under different conditions for different reactants.
1 H NMR (500 MHz) and 13 C NMR (126 MHz) spectra were tested on Varian Liquid State NMR instruments. If not specified, the nuclear magnetism uses DMSO-d 6 or CDCl 3 containing 0.1% TMS as a solvent, wherein 1 H NMR spectrum uses CDCl 3 as a solvent, and the solvent has internal standard tetramethylsilane, and chemical shift refers to tetramethylsilane (delta=0.00 ppm); otherwise, if CDCl 3 is used as solvent, 1 H NMR spectrum chemical shift is followed by reference to residual solvent (δ=7.26 ppm); when DMSO-d 6 was used as a solvent, TMS (δ=0.00 ppm) or residual DMSO peak (δ=2.50 ppm) or residual water peak (δ=3.33 ppm) was used as an internal standard. 13 CDCl 3 (δ=77.00 ppm) or DMSO-d 6 (δ=39.52 ppm) was used as internal standard in the C NMR spectrum. 1 H NMR spectrum data: s= singlet, single peak; d= doublet, double peak; t=triplet, triplet; q= quartet, quadruple; p=quintet, quintet; m= multiplet, multiple peaks; br=broad, broad peak.
Synthetic route
The general synthesis steps are as follows:
example 1: the luminescent material Pt (bp-1) can be synthesized as follows:
(1) Synthesis of intermediate A-OH: to a dry three-necked flask with a magnetic stirrer was added o-bromobiphenyl (2.56 g,11.0mmol,1.7 eq.) and tetrahydrofuran (70 mL) under nitrogen. The reaction apparatus was placed in an ethanol bath, cooled to-78℃with liquid nitrogen, then n-butyllithium (7.00 mL,11.00mmol,1.7 eq., 1.60mol/L n-hexane solution) was slowly added dropwise thereto, and after 3 hours of reaction, 3-bromophenyl-2-pyridinemethanone (1.80 mg,6.90mmol,1.00 eq.) was further added thereto, and stirred at room temperature for 24 hours. The reaction solution was quenched with saturated solution of ammonium chloride, extracted three more times with ethyl acetate, and the aqueous layer was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was filtered and the solvent was distilled off under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate=20:1-10:1, to obtain product A-OH, oily colorless transparent liquid 2.60g, yield 90％.1H NMR(500MHz,DMSO):δ6.71(s,1H),6.88-6.86(m,3H),6.95(t,J＝7.0Hz,2H),7.03-6.98(m,2H),7.06(ddd,J＝1.0,5.0,6.0Hz,1H),7.14(t,J＝8.0Hz,1H),7.25(td,J＝1.5,7.5Hz,1H),7.33-7.29(m,3H),7.44-7.42(m,1H),7.47(td,J＝1.5,7.5Hz,1H),7.59(t,J＝2.0Hz,1H),8.35(dq,J＝0.5,4.5Hz,1H).
(2) Synthesis of intermediate a: to a dry three-necked flask with a magnetic stirrer was added A-OH (1.00 g,2.40mmol,1.00 eq.) and acetic acid (25 mL), followed by concentrated sulfuric acid (1 mL) and acetic anhydride (1 mL). The three-neck flask was placed in an oil bath with magnetic stirring, and stirred at 130℃for reaction for 12 hours, and thin-layer chromatography was monitored until the reaction of the starting materials was completed. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the pH was adjusted to weakly alkaline with saturated sodium carbonate solution. Then ethyl acetate was added to extract three times, the aqueous layer was extracted twice with ethyl acetate, the combined organic phases were dried over anhydrous sodium sulfate, and the filtrate was filtered and the solvent was distilled off under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate=10:1-5:1, yielding a, 920mg of white solid, yield 96％.1H NMR(500MHz,DMSO-d6):δ7.04-6.98(m,3H),7.20(t,J＝7.5Hz,1H),7.28(ddd,J＝6.0,5.0,1.0Hz,1H),7.35(td,J＝7.5,1.0Hz,2H),7.40(ddd,J＝3.0,2.0,1.0Hz,1H),7.44(td,J＝7.5,1.0Hz,2H),7.57(d,J＝7.5Hz,2H),7.66(td,J＝7.5,2.0Hz,1H),7.95(d,J＝7.5Hz,2H),8.59(ddd,J＝2.5,1.5,0.5Hz,1H).
(3) Synthesis of intermediate A-B: to a dry, sealed tube with magnetic stirrer was added A-Br (800 mg,2.00mmol,1.00 eq.) and bis-pinacolato borate (780 mg,3.00mmol,1.50 eq.) and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (88 mg,0.12mmol,6 mol%), potassium acetate was added rapidly, followed by three nitrogen changes and dimethyl sulfoxide (20 mL) was added under nitrogen protection. Then the tube is put into an oil bath pot with magnetic stirring, stirred and reacted for 1 day in the oil bath pot with the temperature of 70 ℃, and the thin layer chromatography is monitored until the reaction of the raw materials is completed. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed twice with water and the aqueous layer was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed by distillation from the filtrate under reduced pressure after filtration, and the crude product was separated by silica gel chromatography, eluent: petroleum ether/ethyl acetate/dichloromethane=20:1:1-10:1:1 to give a-B, 840mg of white solid, yield 95％.1H NMR(500MHz,CDCl3):δ1.27(s,12H),7.05(d,J＝8.0Hz,1H),7.08(dq,J＝2.0,1.5Hz,1H),7.21-7.16(m,2H),7.29(td,J＝7.5,1.0Hz,2H),7.38(td,J＝7.5,1.0Hz,2H),7.51(t,J＝7.0Hz,1H),7.57(s,1H),7.61(d,J＝7.5Hz,2H),7.67(d,J＝7.0Hz,1H),7.78(d,J＝7.5Hz,2H),8.69(d,J＝3.5Hz,1H).
(4) Synthesis of ligand L (bp-1): to a dry three-necked flask with a magnetic stirrer were added A-Br (376 mg,0.95mmol,1.05 eq.), A-B (400 mg,0.90mmol,1.00 eq.), tetrakis triphenylphosphine palladium (52 mg,0.045mmol,5 mol%) and potassium carbonate (247 mg,1.80mmol,2.0 eq.). Nitrogen was then purged three times and 1, 4-dioxane (12 mL) and water (3 mL) were added under nitrogen. And then the three-neck flask is placed into an oil bath pot with magnetic stirring, the reaction is stirred for 24 hours at 90 ℃, and the reaction of the raw materials is monitored by thin layer chromatography. The reaction was cooled to room temperature, and the solvent was removed by distillation under the reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate/dichloromethane=10:1:1-5:1:1, yielding L (bp-1), 500mg of white solid in yield 87％.1H NMR(500MHz,CDCl3):δ6.96(d,J＝7.5Hz,2H),7.06(s,2H),7.10(s,2H),7.20-7.17(m,4H),7.23(d,J＝7.5Hz,2H),7.27(t,J＝7.5Hz,4H),7.39(t,J＝7.5Hz,4H),7.50(t,J＝7.5Hz,2H),7.56(d,J＝7.5Hz,4H),7.77(d,J＝7.5Hz,4H),8.67(s,2H).
(5) Synthesis of Pt (bp-1): to a dry three-necked flask with a magnetic stirrer were added L (bp-1) (200 mg,0.31mmol,1.00 eq.) and platinum dichloride (88 mg,0.33mmol,1.05 eq.) followed by three nitrogen exchanges and benzonitrile (17 mL) under nitrogen blanket. The three-neck flask was placed in an oil bath with magnetic stirring, and the reaction was stirred at 180℃for 3 days, and the reaction of the raw materials was monitored by thin layer chromatography. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/dichloromethane=1:1-1:2 to give 85mg of yellow solid in yield 32％.1H NMR(500MHz,DMSO-d6):δ6.15(d,J＝7.5Hz,2H),6.58(t,J＝7.5Hz,2H),7.17(dd,J＝21.0,8.0Hz,6H),7.32(s,2H),7.68-7.55(m,8H),7.96-7.92(m,4H),8.13(s,2H),8.83(d,J＝4.5Hz,2H),9.42(s,2H).
Example 2: the luminescent material Pt (bp-2) can be synthesized as follows:
(1) Synthesis of intermediate A-tOH: to a dry three-necked flask with a magnetic stirrer was added 2-bromo-4, 4' -di-tert-butylbiphenyl (1.26 g,3.63mmol,1.0 eq.) and tetrahydrofuran (40 mL) was added under nitrogen. The reaction apparatus was placed in an ethanol bath, cooled to-78℃with liquid nitrogen, then n-butyllithium (2.30 mL,3.63mmol,1.0 eq., 1.60mol/L n-hexane solution) was slowly added dropwise thereto, and after 3 hours of reaction, 3-bromophenyl-2-pyridinemethanone (1.00 mg,3.80mmol,1.05 eq.) was further added thereto, and stirred at room temperature for 24 hours. The reaction solution was quenched with saturated solution of ammonium chloride, extracted three more times with ethyl acetate, and the aqueous layer was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, and the filtrate was filtered and the solvent was distilled off under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate=40:1-20:1, to give product a-thoh, 1.50g of oily colorless transparent liquid, yield 78％.1H NMR(500MHz,CDCl3):δ1.21(s,9H),1.25(s,9H),6.89(d,J＝8.0Hz,2H),7.06-7.00(m,4H),7.13-7.07(m,4H),7.28(t,J＝6.5Hz,2H),7.34(dd,J＝8.0,1.5Hz,1H),7.50(t,J＝7.5Hz,1H),7.54(s,1H),8.37(d,J＝4.5Hz,1H).
(2) Synthesis of intermediate A-tBr: to a dry three-necked flask with a magnetic stirrer was added A-tBr (1.50 g,2.84mmol,1.00 eq.) and acetic acid (25 mL), followed by concentrated sulfuric acid (1.2 mL) and acetic anhydride (1 mL). The three-neck flask was placed in an oil bath with magnetic stirring, and stirred at 130℃for reaction for 12 hours, and thin-layer chromatography was monitored until the reaction of the starting materials was completed. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure, and the pH was adjusted to weakly alkaline with saturated sodium carbonate solution. Then ethyl acetate was added to extract three times, the aqueous layer was extracted twice with ethyl acetate, the combined organic phases were dried over anhydrous sodium sulfate, and the filtrate was filtered and the solvent was distilled off under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate=20:1-10:1, to obtain product A-tBr, oily colorless transparent liquid 1.5g, yield 99％.1H NMR(500MHz,CDCl3):δ1.30(s,18H),6.99(d,J＝6.0Hz,1H),7.16(s,1H),7.25-7.21(m,2H),7.40(dd,J＝8.0,1.5Hz,2H),7.51(s,1H),7.60(s,1H),7.65(d,J＝8.0Hz,3H),7.68-7.66(m,2H),8.71(s,1H).
(3) Synthesis of intermediate A-tB: to a dry tube sealer with magnetic stirrer was added A-tBr (400 mg,0.78mmol,1.00 eq.) of bispinacol borate (298 mg,1.17mmol,1.50 eq.) of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride (35 mg,0.05mmol,6.0 mol%), potassium acetate was added rapidly, followed by three nitrogen changes and dimethyl sulfoxide (12 mL) under nitrogen protection. Then the tube is put into an oil bath pot with magnetic stirring, stirred and reacted for 2 days in the oil bath pot with the temperature of 70 ℃, and the thin layer chromatography is monitored until the reaction of the raw materials is finished. The reaction was cooled to room temperature, diluted with ethyl acetate, the organic phase was washed twice with water and the aqueous layer was extracted twice with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, the solvent was removed by distillation from the filtrate under reduced pressure after filtration, and the crude product was separated by silica gel chromatography, eluent: petroleum ether/ethyl acetate/dichloromethane=20:1:1-10:1:1 to give 390mg of white solid in yield 89％.1H NMR(500MHz,CDCl3):δ1.25(s,12H),1.30(s,18H),7.00(d,J＝5.5Hz,1H),7.16(s,1H),7.25-7.21(m,2H),7.40(dd,J＝8.0,1.5Hz,2H),7.51(s,1H),7.60(s,1H),7.64(s,1H),7.68-7.64(m,4H),8.71(s,1H).
(4) Synthesis of ligand L (bp-2): A-tBr (192 mg,0.38mmol,1.05 eq.) A-tB (200 mg,0.36mmol,1.00 eq.), palladium tetraphenylphosphine (21 mg,0.018mmol,5 mol%) and potassium carbonate (99 mg,0.72mmol,2.0 eq.) were added to a dry three-neck flask with a magnetic stirrer. Nitrogen was then purged three times and 1, 4-dioxane (8 mL) and water (2 mL) were added under nitrogen. And then the three-neck flask is placed into an oil bath pot with magnetic stirring, the reaction is stirred for 24 hours at 90 ℃, and the reaction of the raw materials is monitored by thin layer chromatography. The reaction was cooled to room temperature, and the solvent was removed by distillation under the reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate/dichloromethane=20:1:2-10:1:2 to give L (bp-2), 291mg of white solid, yield 94％.1H NMR(500MHz,DMSO-d6):δ1.20(s,36H),6.79(dt,J＝1.5,7.5Hz,2H),6.94(d,J＝8.0Hz,2H),7.09(t,J＝1.5Hz,2H),7.22(t,J＝9.0Hz,2H),7.28-7.23(m,4H),7.42(dd,J＝1.5,9.0Hz,4H),7.48(d,J＝1.5Hz,4H),7.64(td,J＝1.5,7.5Hz,2H),7.77(d,J＝8.0Hz,4H),8.51-8.50(m,2H).
(5) Synthesis of Pt (bp-2): to a dry three-necked flask with a magnetic stirrer were added L (bp-2) (250 mg,0.29mmol,1.00 eq.) and platinum dichloride (81 mg,0.30mmol,1.05 eq.) followed by three nitrogen exchanges and benzonitrile (17 mL) under nitrogen blanket. The three-neck flask was placed in an oil bath with magnetic stirring, and the reaction was stirred at 180℃for 1 day, and the reaction of the raw materials was monitored by thin layer chromatography. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/dichloromethane=1:2-1:4 to give 233mg of yellow solid in yield 76％.1H NMR(500MHz,DMSO-d6):δ1.05(s,18H),1.40(s,18H),6.13(dd,J＝8.5,1.0Hz,2H),6.56(t,J＝7.0Hz,2H),7.05-7.03(m,2H),7.16-7.15(m,2H),7.33(dd,J＝8.0,1.5Hz,2H),7.52-7.48(m,4H),7.69(dd,J＝8.0,1.5Hz,2H),7.73(d,J＝8.0Hz,2H),7.92-7.89(m,2H),7.98(d,J＝8.5Hz,2H),8.87-8.86(m,2H),9.33(d,J＝1.5Hz,2H).
Example 3: the luminescent materials Pt 1-t may be synthesized as follows:
(1) Synthesis of ligand L (bp-1-t): to a dry three-necked flask with a magnetic stirrer were added A-tBr (400 mg,0.78mmol,1.0 eq.), A-B (365 mg,0.82mmol,1.05 eq.), tetrakis triphenylphosphine palladium (45 mg,0.039mmol,5.0 mol%) and potassium carbonate (216 mg,1.56mmol,2.0 eq.). Nitrogen was then purged three times and 1, 4-dioxane (12 mL) and water (3 mL) were added under nitrogen. And then the three-neck flask is placed into an oil bath pot with magnetic stirring, the reaction is stirred for 24 hours at 90 ℃, and the reaction of the raw materials is monitored by thin layer chromatography. The reaction was cooled to room temperature, and the solvent was removed by distillation under the reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/ethyl acetate/dichloromethane=20:1:3-10:1:3, yielding L (bp-1-t), 530mg of white solid, yield 91％.1H NMR(500MHz,DMSO-d6):δ1.21(s,18H),6.82(dt,J＝8.0,1.5Hz,1H),6.88(dt,J＝8.0,1.5Hz,1H),6.96(t,J＝2.0Hz,1H),6.98(dt,J＝3.5,1.0Hz,1H),7.00(dt,J＝3.5,1.0Hz,1H),7.07(t,J＝2.0Hz,1H),7.31-7.20(m,8H),7.44-7.40(m,6H),7.54(d,J＝1.5Hz,2H),7.62(td,J＝7.5,2.0Hz,1H),7.68(td,J＝8.0,2.0Hz,1H),7.78(d,J＝8.0Hz,2H),7.93-7.91(m,2H),8.46(ddd,J＝5.0,2.0,1.0Hz,1H),8.57(ddd,J＝5.0,2.0,1.0Hz,1H).
(2) Synthesis of Pt (bp-1-t): to a dry three-necked flask with a magnetic stirrer were added L (bp-1-t) (300 mg,0.40mmol,1.00 eq.) and platinum dichloride (114 mg,0.42mmol,1.05 eq.) followed by three nitrogen exchanges and benzonitrile (18 mL) under nitrogen. The three-neck flask was placed in an oil bath with magnetic stirring, and the reaction was stirred at 180℃for 3 days, and the reaction of the raw materials was monitored by thin layer chromatography. After the reaction was cooled to room temperature, the solvent was removed by distillation under reduced pressure. Separating the crude product with silica gel chromatographic column, eluting with eluent: petroleum ether/dichloromethane=2:1-1:1 to give 271mg of yellow solid in yield 72％.1H NMR(500MHz,DMSO-d6):1.03(s,9H),1.40(s,9H),6.13(ddd,J＝8.0,4.0,1.0Hz,2H),6.56(t,J＝7.5Hz,2H),7.08-7.07(m,1H),7.12-7.09(m,2H),7.18-7.15(m,2H),7.30(td,J＝7.5,1.0Hz,1H),7.33(dd,J＝8.0,1.5Hz,1H),7.49(ddd,J＝7.5,5.5,1.0Hz,1H),7.54(ddd,J＝7.5,9.0,1.5Hz,1H),7.64-7.60(m,3H),7.70-7.66(m,2H),7.73(d,J＝8.0Hz,1H),7.94-7.88(m,3H),7.79(d,J＝8.5Hz,1H),8.13(d,J＝8.5Hz,1H),8.86-8.83(m,2H),9.35(d,J＝7.5Hz,1H),9.39(d,J＝1.5Hz,1H).
While the invention has been described with respect to the above embodiments, it should be noted that modifications can be made by those skilled in the art without departing from the inventive concept, and these are all within the scope of the invention.
Description of Performance evaluation
The following were carried out photophysical test analysis and theoretical calculation study of the complexes prepared in the above examples of the present invention.
Photophysical test: the emission spectra were all tested on a HITACHI F-7000 spectrometer, and the emission spectra of the luminescent materials synthesized in examples 1, 2 and 3 are shown in FIGS. 1-3. Test conditions of the emission spectrum of the complex luminescent material: all samples were tested at room temperature as dilute solutions of methylene chloride (chromatographic grade) (10 -5-10-6 M). The tests were performed on both steady state emission experiments and lifetime measurements using Horiba Jobin Yvon FluoroLog-3 spectrometers. Test conditions of low-temperature (77K) emission spectrum and life of the complex luminescent material: measured in a liquid nitrogen cooled solution of 2-methyltetrahydrofuran (2-MeTHF).
Theoretical calculation: the band gap (Eg), LUMO and HOMO values of the complex were calculated theoretically using Gaussian 09 software package, the geometry of the ground state (S0) molecule was optimized using Density Functional Theory (DFT), DFT was performed using B3LYP functional, wherein C, H, O and N atoms use the 6-31G (d) group and Pt atoms use the LANL2DZ group.
Photophysical analysis data and analysis
As can be seen from the photo-induced emission spectra and photophysical data of the accompanying drawings 1,2 and 3, the complexes Pt (bp-1), pt (bp-2) and Pt (bp-1-t) all show strong green light emission, and can be used as green light luminescent materials. Through the regulation and control of substituent groups in the ligand, the derivative is found to have green light emission with higher color purity, and the substituent groups with large steric hindrance may have larger effects on the solubility of the complex, weakening intermolecular pi-pi accumulation and improving the quantum efficiency of the device. At room temperature in methylene dichloride solution, pt (bp-1), pt (bp-2) and Pt (bp-1-t) all have main peak emission spectrums with narrow half peak widths, which indicates that the metal-to-ligand charge transfer state (MLCT) component in the molecular excited state of the material is more, so that the service life of the excited state is shortened, the improvement of the crossing rate between the molecular systems of the phosphorescent material is facilitated, and the quantum efficiency of the material is further improved.
TABLE 1 data list of photophysical properties of tetradentate 6/5/6 cyclometalated platinum (II) complex phosphorescent materials
Note that: lambda is the emission wavelength; τ obs is the excited state lifetime of the material.
Fig. 1 to 3 show emission spectra of three luminescent materials in table 1 at room temperature in methylene chloride solution. From the data, the four-tooth ring metal platinum (II) complex with the spirofluorene-spirofluorene biphenyl structure has the maximum emission peak of 504-505nm in methylene dichloride solution at room temperature, is a green light luminescent material, has the quantum efficiency of more than 50%, and can quench luminescence due to the problem of oxygen infiltration when tested in a nitrogen atmosphere due to the condition limitation, and the data is low. FIG. 4 is a comparison of emission spectra of the three luminescent materials synthesized in examples 1, 2 and 3 in methylene chloride solution at room temperature, showing that the introduction of substituents on spirofluorene has substantially no effect on its emission wavelength and shoulder.
DFT theoretical calculation data and analysis
From the data of FIGS. 5-1, 5-2 and 5-3, the calculated HOMO and LUMO orbital distributions of the complexes Pt (bp-1), pt (bp-2), pt (bp-1-t) and their derivatives are shown as separate modes. Wherein the HOMO orbitals are uniformly distributed on the biphenyl structure, the LUMO orbitals are uniformly distributed on the pyridine ring, and the spirofluorene structure does not participate in the composition of the HOMO or LUMO orbitals. Furthermore, there is no significant difference in the orbital distribution of these platinum complexes, with very similar HOMO, LUMO energy levels.
The band gap values (Eg) of the complexes Pt (bp-1), pt (bp-2), pt (bp-1-t) and Pt-3, pt (bp-1) 0 are basically the same. The band gap values (Eg) of the complexes Pt-4, pt-5, pt-7 and Pt-8 are higher than those of the complex Pt (bp-1), which shows that the LUMO energy level of the material can be reduced by introducing the tertiary butyl group with a strong electron donating group at the para position of pyridine N; however, the introduction of the strong electron withdrawing group trifluoromethyl or N-heterobiphenyl on the biphenyl has no obvious influence on the HOMO energy level of the material. The band gap values (Eg) of the complexes Pt-6, pt-9 and Pt (bp-1) 2 are lower than those of the complexes Pt (bp-1), which shows that the LUMO energy level of the material can be greatly reduced by introducing a trifluoromethyl or N-heterobiphenyl which is a strong electron-withdrawing group at the para position of pyridine N.
TABLE 2 energy level data calculated by Complex DFT theory
| Complex compound | EHOMO/eV | ELUMO/eV | Eg/eV |
| Pt(bp-1) | -4.59 | -1.42 | 3.17 |
| Pt-3 | -4.38 | -1.23 | 3.15 |
| Pt-4 | -5.03 | -1.51 | 3.52 |
| Pt-5 | -5.08 | -1.52 | 3.56 |
| Pt-6 | -5.39 | -2.34 | 3.05 |
| Pt(bp-1-t) | -4.57 | -1.41 | 3.16 |
| Pt(bp-2) | -4.54 | -1.38 | 3.16 |
| Pt-7 | -5.08 | -1.52 | 3.56 |
| Pt-8 | -5.04 | -1.59 | 3.45 |
| Pt-9 | -4.81 | -2.12 | 2.69 |
| Pt(bp-1)0 | -5.32 | -2.14 | 3.18 |
| Pt(bp-1)1 | -4.66 | -1.44 | 3.22 |
| Pt(bp-1)2 | -4.55 | -1.87 | 2.68 |
Note that: FIGS. 5-1, 5-2 and 5-3 show the front orbital distribution, highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) distributions of the complex, eg being the band gap value.
By introducing substituents, such as alkyl substituents or heteroatom substituents, into the luminescent molecule, the highest molecular occupied orbital (HOMO) and the lowest molecular unoccupied orbital (LUMO) energy levels of the luminescent material thereof are changed, and at the same time, the energy gap Eg between the HOMO and LUMO orbitals is further adjusted, the emission spectral properties of the Pt (bp-1) -series complex can be adjusted, such as making it wider or narrower, or making its emission wavelength red-shifted or blue-shifted. This can meet the need for improved performance in light emission and absorption applications.
OLED device
In an organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emitted. The complex of the present invention represented by the general formula (I) can be applied as a phosphorescent light-emitting material to an organic light-emitting element excellent in organic photoluminescent element, organic electroluminescent element, and the like. A schematic structure of a specific organic light emitting element is shown in fig. 6. In fig. 6, a total of 7 layers from bottom to top represent a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode in this order, wherein the light emitting layer is a mixed layer in which a guest material is doped into a host material.
The phosphorescent light-emitting material disclosed by the invention is used as a guest material to be doped into a host material to prepare a light-emitting layer, and can be applied to an OLED device, and the structure is expressed as follows:
ITO/HATCN (10 nm)/TAPC (65 nm)/host material Pt (bp-1) (10 wt.%,35 nm)/PPT (2 nm)/Bepp 2:Li 2CO3(30nm)/Li2CO3/Al (device structure not optimized).
Wherein, ITO is a transparent anode; hat is a hole injection layer, TAPC is a hole transport layer, host materials are mCBP and PYD2 respectively, PPT is a hole blocking layer, bepp2:li 2CO3 is an electron transport layer, li 2CO3 is an electron injection layer, and Al is a cathode. The numbers in brackets in nanometers (nm) are the thickness of the film.
The molecular formula of the application material in the device is as follows:
pt (bp-1) did not decompose during sublimation purification, indicating its good stability. As can be seen from the accompanying figures 7 and 8, the OLED device doped with the 6/5/6 four-tooth ring metal platinum (II) complex phosphorescent material Pt (bp-1) based on the spirofluorene-spirofluorene biphenyl structure is green light, has higher quantum efficiency (more than 10%) and luminous brightness, and the maximum brightness of the device taking mCBP and PYD2 as main materials can reach 10734cd/m 2 and 16644cd/m 2 respectively.
In the above embodiments, the light-emitting layer may include one or more of the platinum (II) or palladium (II) complexes provided by the present invention, optionally together with a host material. The material of the injection layer may include EIL (electron injection layer), HIL (hole injection layer) and CPL (cathode capping layer), which may be in the form of a single layer or dispersed in an electron or hole transport material. The host material may be any suitable host material known in the art. The emission color of an OLED is determined by the emission energy (optical energy gap) of the light-emitting layer material, which can be tuned as described above by tuning the electron structure of the emissive platinum (II) complex and/or the host material. The hole transporting material in the HTL layer and the electron transporting material in the ETL layer may comprise any suitable hole transporter known in the art.
In addition, the structure is an example of one application of the phosphorescent material of the present invention, and does not constitute a limitation of the specific OLED device structure of the phosphorescent material of the present invention, nor is the phosphorescent material limited to the compounds represented in the examples.
In addition, embodiments of the present invention also provide an optical device comprising one or more of the four-ring metal platinum (II) or palladium (II) complex phosphorescent materials.
Optionally, the device comprises a full color display.
Optionally, the device is a photovoltaic device.
Optionally, the device is a light emitting display device.
Optionally, the device comprises an organic light emitting diode.
Optionally, the device comprises a phosphorescent organic light emitting diode.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of carrying out the invention and that various changes in form and details may be made therein without departing from the spirit and scope of the invention. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.
Claims (9)
1. The 6/5/6 four-tooth ring metal platinum complex based on the spirofluorene-spirofluorene structure is characterized by having a structure shown in a general formula (I):
Wherein:
The metal M is Pt;
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11、Y12、Y13 And Y 14 each independently represents CH or N;
R 1、R2、R3、R4、R5、R6、R7 and R 8 each independently represent mono-, di-, tri-, tetra-or unsubstituted substituents, and R 1、R2、R3、R4、R5、R6、R7 and R 8 each independently are hydrogen, deuterium, aryl, cycloalkyl, alkyl, halogen, alkoxy, haloalkyl.
2. A spirofluorene-spirofluorene structure based 6/5/6 tetradentate ring metal platinum complex according to claim 1, having a structure of one of the following:
Wherein, the metal M is Pt,
3. The spirofluorene-spirofluorene structure-based 6/5/6 four-tooth ring metal platinum complex according to claim 1 or 2, wherein the platinum complex has a spirofluorene-spirofluorene structure based on biphenyl and its derivative linkage, and the linking atoms on both sides of the ligand are only carbon atoms.
4. Use of a 6/5/6 four-ring metal platinum complex based on a spirofluorene-spirofluorene structure as claimed in claim 1 or 2 as electroluminescent material or photoluminescent material.
5. A device comprising the spirofluorene-spirofluorene structure-based 6/5/6 tetradentate metal platinum complex according to claim 1 or 2.
6. The device of claim 5, wherein the device is a full color display, a photovoltaic device, a light emitting display device, or an organic light emitting diode.
7. The device according to claim 5, characterized by comprising at least one cathode, at least one anode and at least one light-emitting layer, at least one of said light-emitting layers comprising the spirofluorene-spirofluorene structure based 6/5/6 tetradentate metal platinum complex according to claim 1 or 2.
8. The device according to claim 5, wherein the device is an organic light emitting diode comprising the spirofluorene-spirofluorene based 6/5/6-tetradentate metal platinum complex and the corresponding host material in a light emitting layer, wherein the mass percentage of the metal platinum complex is 1% to 50%.
9. A display or lighting device, characterized in that it comprises a device according to any one of claims 5 to 8.
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