JP5798309B2 - Aluminum complex with fluorine-substituted dibenzoylmethanide as a ligand - Google Patents
Aluminum complex with fluorine-substituted dibenzoylmethanide as a ligand Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 53
- 239000003446 ligand Substances 0.000 title description 24
- -1 fluorine-substituted dibenzoylmethanide Chemical class 0.000 title description 22
- 125000001153 fluoro group Chemical group F* 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 13
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 6
- 238000001663 electronic absorption spectrum Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- OYZWEOORLJBPMA-UHFFFAOYSA-N 3,5-difluorobenzoyl chloride Chemical compound FC1=CC(F)=CC(C(Cl)=O)=C1 OYZWEOORLJBPMA-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- RZCYUOWKJNUVBF-UHFFFAOYSA-M 3-oxo-1,3-diphenylprop-1-en-1-olate Chemical compound C=1C=CC=CC=1C([O-])=CC(=O)C1=CC=CC=C1 RZCYUOWKJNUVBF-UHFFFAOYSA-M 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- AELMDUZWKHVPIF-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzoyl chloride Chemical compound FC1=CC(F)=C(F)C(C(Cl)=O)=C1F AELMDUZWKHVPIF-UHFFFAOYSA-N 0.000 description 1
- SIFIJQFBERMWMU-UHFFFAOYSA-N 2,4,6-trifluorobenzoyl chloride Chemical compound FC1=CC(F)=C(C(Cl)=O)C(F)=C1 SIFIJQFBERMWMU-UHFFFAOYSA-N 0.000 description 1
- QRHUZEVERIHEPT-UHFFFAOYSA-N 2,6-difluorobenzoyl chloride Chemical compound FC1=CC=CC(F)=C1C(Cl)=O QRHUZEVERIHEPT-UHFFFAOYSA-N 0.000 description 1
- YRUNCQNKZIQTEO-UHFFFAOYSA-N 3,4,5-trifluorobenzoyl chloride Chemical compound FC1=CC(C(Cl)=O)=CC(F)=C1F YRUNCQNKZIQTEO-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Description
本発明は、フッ素置換ジベンゾイルメタニドを配位子とする発光特性を有し、低濃度分散型のＥＬ素子として有用な新規なアルミニウム錯体に関する。 The present invention relates to a novel aluminum complex having a light emission characteristic having a fluorine-substituted dibenzoylmethanide as a ligand and useful as a low concentration dispersion type EL device.
本発明者は、先にジベンゾイルメタン−金属（白金、銅、パラジウム）錯体またはその誘導体とビス（ペンタフルオロベンゾイル）メタン−金属（白金、銅、パラジウム）錯体またはその誘導体とを含む錯体クラスター、及び錯体結晶について特許出願をしている（特開２００９−０２３９１８号公報；特許文献１）。
また、本発明者らは、トリス（ペンタフルオロジベンゾイル）メタン−アルミニウム錯体及びその錯体を出発原料とするビス（ペンタフルオロジベンゾイル）メタン−金属（コバルト、ニッケル、銅）錯体の合成と結晶構造について報告している（「Synthesis and Crystal Structures of Fluorinated β-Diketonate Metal(Al3+, Co2+, Ni2+, and Cu2+) Complexes」（Bull. Chem.，Soc. Jpn. Vol. 82, No. 1, 96-98 (2009)；非特許文献１）。
The inventor previously prepared a complex cluster containing a dibenzoylmethane-metal (platinum, copper, palladium) complex or a derivative thereof and a bis (pentafluorobenzoyl) methane-metal (platinum, copper, palladium) complex or a derivative thereof, And a patent application for the complex crystal (Japanese Patent Laid-Open No. 2009-023918; Patent Document 1).
In addition, the present inventors also synthesized and crystal structure of tris (pentafluorodibenzoyl) methane-aluminum complex and bis (pentafluorodibenzoyl) methane-metal (cobalt, nickel, copper) complex starting from the complex. (“Synthesis and Crystal Structures of Fluorinated β-Diketonate Metal (Al 3+ , Co 2+ , Ni 2+ , and Cu 2+ ) Complexes” (Bull. Chem., Soc. Jpn. Vol. 82 , No. 1, 96-98 (2009); Non-Patent Document 1).
本発明者は、トリス（ジベンゾイル）メタン−アルミニウム錯体について、ベンゾイル基の水素原子の任意の数をフッ素原子に置換した錯体を合成し、それら錯体中のフッ素原子の置換位置及び数とその発光スペクトルとの関係について調べた。その結果、フッ素置換の位置及び数を選択することにより、発光波長を制御（微調節）できることを確認した。 The present inventor synthesizes a tris (dibenzoyl) methane-aluminum complex in which any number of hydrogen atoms in the benzoyl group is substituted with fluorine atoms, and the position and number of fluorine atoms in the complex and the emission spectrum thereof. We investigated the relationship with. As a result, it was confirmed that the emission wavelength can be controlled (finely adjusted) by selecting the position and number of fluorine substitutions.
本発明は、下記の新規なトリス（フッ素原子置換ジベンゾイル）メタン−アルミニウム錯体を提供する。 The present invention provides the following novel tris (fluorine atom-substituted dibenzoyl) methane-aluminum complex.
１.一般式（Ｉ）
で示されるアルミニウム錯体。
２．一般式（Ｉ）において、Ｒ12、Ｒ14、Ｒ22及びＲ24がフッ素原子であり、Ｒ11、Ｒ13、Ｒ15、Ｒ21、Ｒ23及びＲ25が水素原子である、前項１に記載のアルミニウム錯体。
３．一般式（Ｉ）において、Ｒ11、Ｒ15、Ｒ21及びＲ25がフッ素原子であり、Ｒ12、Ｒ13、Ｒ14、Ｒ22、Ｒ23及びＲ24が水素原子である、前項１に記載のアルミニウム錯体。
４．一般式（Ｉ）において、Ｒ11、Ｒ13、Ｒ15、Ｒ21、Ｒ23及びＲ25がフッ素原子であり、Ｒ12、Ｒ14、Ｒ22及びＲ24が水素原子である、前項１に記載のアルミニウム錯体。
５．一般式（Ｉ）において、Ｒ12、Ｒ13、Ｒ14、Ｒ22、Ｒ23及びＲ24がフッ素原子であり、Ｒ11、Ｒ15、Ｒ21及びＲ15が水素原子である、前項１に記載のアルミニウム錯体。
６．一般式（Ｉ）において、Ｒ11、Ｒ12、Ｒ14、Ｒ15、Ｒ21、Ｒ22、Ｒ24及びＲ25がフッ素原子であり、Ｒ13及びＲ23が水素原子である、前項１に記載のアルミニウム錯体。
７．前項１〜６のいずれかに記載のアルミニウム錯体を含む発光材料。
８．前項７に記載の発光材料を含むＥＬ素子。
1. General formula (I)
An aluminum complex represented by
2. In the general formula (I), R 12 , R 14 , R 22 and R 24 are fluorine atoms, and R 11 , R 13 , R 15 , R 21 , R 23 and R 25 are hydrogen atoms. The aluminum complex described.
3. In the general formula (I), R 11 , R 15 , R 21 and R 25 are fluorine atoms, and R 12 , R 13 , R 14 , R 22 , R 23 and R 24 are hydrogen atoms. The aluminum complex described.
4). In the general formula (I), R 11 , R 13 , R 15 , R 21 , R 23 and R 25 are fluorine atoms, and R 12 , R 14 , R 22 and R 24 are hydrogen atoms. The aluminum complex described.
5. In the general formula (I), R 12 , R 13 , R 14 , R 22 , R 23 and R 24 are fluorine atoms, and R 11 , R 15 , R 21 and R 15 are hydrogen atoms. The aluminum complex described.
6). In the general formula (I), R 11 , R 12 , R 14 , R 15 , R 21 , R 22 , R 24 and R 25 are fluorine atoms, and R 13 and R 23 are hydrogen atoms. The aluminum complex described.
7). A light emitting material containing the aluminum complex according to any one of 1 to 6 above.
8). 8. An EL device comprising the light emitting material according to item 7.
本発明は、フッ素置換ジベンゾイルメタニドを配位子とする新規なアルミニウム錯体を提供したものである。
本発明のアルミニウム錯体は、フッ素の置換位置及び数が変わることで、その発光波長が段階的に変化し、溶液では白色、固体では白色から黄色の強い発光を示す。フッ素置換化合物はフッ素間の反発作用、フッ素を介した作用（ＣＨ・Ｆ間の作用やアニオン・π電子相互作用など）により分子間で相互に影響を及ぼすことが知られている。従って、フッ素置換ジベンゾイルメタニドを配位子とする本発明のアルミニウム錯体（発光材料）は、フッ素を置換していないものに比べて、有機ポリマーなどに塗布、混入して使用する場合に、フッ素効果により優れた分散性及び溶解性を示し、ポリマーの炭化水素鎖中に効率的に分散させることができるため、低濃度分散型のＥＬ素子として有用である。
The present invention provides a novel aluminum complex having a fluorine-substituted dibenzoylmethanide as a ligand.
In the aluminum complex of the present invention, the emission wavelength changes stepwise by changing the substitution position and the number of fluorine, and the solution emits white light from a solution, and emits strong white to yellow light from a solid. Fluorine-substituted compounds are known to influence each other between molecules due to the repulsive action between fluorine and the action via fluorine (CH-F action, anion-pi-electron interaction, etc.). Therefore, the aluminum complex (light-emitting material) of the present invention having a fluorine-substituted dibenzoylmethanide as a ligand is applied to an organic polymer or the like, compared to those not substituted with fluorine. Since it exhibits excellent dispersibility and solubility due to the fluorine effect and can be efficiently dispersed in the hydrocarbon chain of the polymer, it is useful as a low concentration dispersion type EL device.
以下、本発明について具体的に説明する。
本発明に係るアルミニウム錯体は、下記一般式（Ｉ）
で示される。
Hereinafter, the present invention will be specifically described.
The aluminum complex according to the present invention has the following general formula (I):
Indicated by
すなわち、本発明のアルミニウム錯体は、一般式（II）で示されるジベンゾイルメタン（ＤＢＭ）
本発明のアルミニウム錯体において、ジベンゾイルメタン骨格の（フッ素置換）フェニル基の具体例としては、以下の（１）〜（６）で示されるものが挙げられる。
上記一般式（Ｉ）で示される本発明のアルミニウム錯体の具体例としては、（ｉ）Ｒ12、Ｒ14、Ｒ22及びＲ24がフッ素原子で、Ｒ11、Ｒ13、Ｒ15、Ｒ21、Ｒ23及びＲ25が水素原子であるもの（錯体３ａと略記する。）、（ii）Ｒ11、Ｒ15、Ｒ21及びＲ25がフッ素原子で、Ｒ12、Ｒ13、Ｒ14、Ｒ22、Ｒ23及びＲ24が水素原子であるもの（錯体３ｂと略記する。）、（iii）Ｒ11、Ｒ13、Ｒ15、Ｒ21、Ｒ23及びＲ25がフッ素原子で、Ｒ12、Ｒ14、Ｒ22及びＲ24が水素原子であるもの（錯体４ａと略記する。）、（iv）Ｒ12、Ｒ13、Ｒ14、Ｒ22、Ｒ23及びＲ24がフッ素原子で、Ｒ11、Ｒ15、Ｒ21及びＲ15が水素原子であるもの（４ｂと略記する。）、（v）Ｒ11、Ｒ12、Ｒ14、Ｒ15、Ｒ21、Ｒ22、Ｒ24及びＲ25がフッ素原子で、Ｒ13及びＲ23が水素原子であるもの（錯体５と略記する。）。 Specific examples of the aluminum complex of the present invention represented by the general formula (I) include (i) R 12 , R 14 , R 22 and R 24 are fluorine atoms, and R 11 , R 13 , R 15 , R 21. , R 23 and R 25 are hydrogen atoms (abbreviated as complex 3a), (ii) R 11 , R 15 , R 21 and R 25 are fluorine atoms, R 12 , R 13 , R 14 , R 22 , R 23 and R 24 are hydrogen atoms (abbreviated as complex 3b), (iii) R 11 , R 13 , R 15 , R 21 , R 23 and R 25 are fluorine atoms, R 12 , R 14 , R 22 and R 24 are hydrogen atoms (abbreviated as complex 4a), (iv) R 12 , R 13 , R 14 , R 22 , R 23 and R 24 are fluorine atoms, R 11 , R 15 , R 21 and R 15 are hydrogen atoms (abbreviated as 4b), (v) R 11 , R 12 , R 14 , R 15 , R 21 , R 22 , R 24 and R 25 are A fluorine atom, R 1 3 and R 23 are hydrogen atoms (abbreviated as complex 5).
［アルミニウム錯体の製造方法］
本発明のアルミニウム錯体のうち、(ｉ)〜（iv）の錯体は、以下の通り二段階の工程により合成することが出来る。まず、上記（２）〜（５）で示されるいずれか１つのフッ素置換フェニル基に対応するフッ素置換ベンゾイルクロリドを、室温〜５０℃、好ましくは約４５℃の温度で塩化アルミニウムのテトラクロロエタン等の溶液に加え、その後室温に戻し、酢酸ビニルを加え反応させることにより対応するフッ素置換ジベンゾイル配位子が生成する（第１工程）。得られた配位子を、次に塩化アルミニウムのアルコール溶液、好ましくはメタノールに加えて反応させることで目的とするアルミニウム錯体を製造することができる(第２工程)。
[Method for producing aluminum complex]
Among the aluminum complexes of the present invention, the complexes (i) to (iv) can be synthesized by a two-step process as follows. First, a fluorine-substituted benzoyl chloride corresponding to any one of the fluorine-substituted phenyl groups represented by the above (2) to (5) is used at room temperature to 50 ° C, preferably about 45 ° C, such as tetrachloroethane of aluminum chloride. It adds to a solution and returns to room temperature after that, The corresponding fluorine substitution dibenzoyl ligand is produced | generated by making vinyl acetate add and react (1st process). The obtained ligand is then reacted by adding it to an alcohol solution of aluminum chloride, preferably methanol, to produce the target aluminum complex (second step).
また、(v)の錯体は、上記（６）で示されるフッ素置換フェニル基に対応するフッ素置換ベンゾイルクロリドを、室温〜５０℃、好ましくは約４５℃の温度で塩化アルミニウムのテトラクロロエタン等の溶液に加え、その後室温に戻し、酢酸ビニルを加え反応させる一段階で製造することができる。すなわち、(v)の錯体の場合には、対応するフッ素置換ジベンゾイル配位子を単離することはできないが、これはフッ素置換量が増えると、配位子の安定性が低下するためと考えられる。 The complex of (v) is a solution of fluorine-substituted benzoyl chloride corresponding to the fluorine-substituted phenyl group represented by (6) above in a solution such as tetrachloroethane of aluminum chloride at a temperature of room temperature to 50 ° C., preferably about 45 ° C. In addition, the temperature can be returned to room temperature, and vinyl acetate can be added and reacted in one step. That is, in the case of the complex of (v), the corresponding fluorine-substituted dibenzoyl ligand cannot be isolated, but this is thought to be because the stability of the ligand decreases as the amount of fluorine substitution increases. It is done.
本発明の対応するフッ素置換ジベンゾイル配位子の製造方法で使用する原料のモル比は、特に制限されないが、フッ素置換ベンゾイルクロリド１モルに対して、塩化アルミニウム１モル、酢酸ビニル１モルが好ましい。アルミニウム錯体の製造方法で使用する原料のモル比は、特に制限されないが、配位子１モルに対して、塩化アルミニウムは０．１〜５モルが妥当であり、特に０．３５モルが好ましく、酢酸ビニルは１モルが好ましい。 The molar ratio of the raw materials used in the production method of the corresponding fluorine-substituted dibenzoyl ligand of the present invention is not particularly limited, but 1 mol of aluminum chloride and 1 mol of vinyl acetate are preferable with respect to 1 mol of fluorine-substituted benzoyl chloride. The molar ratio of the raw materials used in the method for producing an aluminum complex is not particularly limited, but 0.1 to 5 mol is appropriate for aluminum chloride with respect to 1 mol of the ligand, and 0.35 mol is particularly preferable. One mole of vinyl acetate is preferred.
本発明の対応するフッ素置換ジベンゾイル配位子の製造方法で使用する溶媒としては、原料を溶解するものであれば特に制限されないが、例えばクロロホルム、ジクロロメタン、１，２，２−テトラクロロエタンが挙げられ、溶媒の沸点が高い点から１，１，２，２−テトラクロロエタン好ましい。配位子と塩化アルミニウムの反応は、原料を溶解するものであれば特に制限されないが、アルコールやジクロロメタンなどのハロゲン溶媒が溶解性に優れている。特に、メタノールが濃縮などの取り扱いが容易で好ましい。 The solvent used in the method for producing the corresponding fluorine-substituted dibenzoyl ligand of the present invention is not particularly limited as long as it dissolves the raw material, and examples thereof include chloroform, dichloromethane, and 1,2,2-tetrachloroethane. In view of the high boiling point of the solvent, 1,1,2,2-tetrachloroethane is preferred. The reaction between the ligand and aluminum chloride is not particularly limited as long as it dissolves the raw material, but a halogen solvent such as alcohol or dichloromethane is excellent in solubility. In particular, methanol is preferable because it is easy to handle such as concentration.
反応温度は、適宜選択できるが、配位子の合成においては室温〜８０℃、特に３０〜５０℃程度が好ましい。室温より低い場合は反応速度が遅いため不利であり、５０℃より高い場合は配位子のオルト位のフッ素が外れて環化反応が起こるため、不要な副生成物が生じる。 Although reaction temperature can be selected suitably, in the synthesis | combination of a ligand, room temperature-80 degreeC, Especially about 30-50 degreeC is preferable. When the temperature is lower than room temperature, the reaction rate is slow, which is disadvantageous. When the temperature is higher than 50 ° C., fluorine at the ortho position of the ligand is removed to cause a cyclization reaction, thereby generating unnecessary by-products.
反応終了後は、常法により溶媒を除去、残留物を抽出し、精製する。得られた錯体はＮＭＲ（核磁気共鳴法）及びＳＩ−ＭＳにより、一般式（Ｉ）で示される各アルミニウム錯体であることが確認できる。 After completion of the reaction, the solvent is removed by a conventional method, and the residue is extracted and purified. The obtained complex can be confirmed to be each aluminum complex represented by the general formula (I) by NMR (nuclear magnetic resonance method) and SI-MS.
本発明のアルミニウム錯体は、発光特性を有する。発光特性は、分光蛍光光度計を用いて測定した電子吸光スペクトルより確認できる。 The aluminum complex of the present invention has luminescent properties. The emission characteristics can be confirmed from an electron absorption spectrum measured using a spectrofluorometer.
本発明のアルミニウム錯体の電子吸光スペクトルより、上記任意に選択したＲ11〜Ｒ15、Ｒ21〜Ｒ25、すなわちジベンゾイルメタニド配位子におけるフェニル基の２〜６位のフッ素の置換位置及び数により発光波長が異なることが確認された。 From the electron absorption spectrum of the aluminum complex of the present invention, R 11 to R 15 , R 21 to R 25 , which are arbitrarily selected from the above, that is, the substitution position of fluorine at the 2-6 position of the phenyl group in the dibenzoylmethanide ligand and It was confirmed that the emission wavelength differs depending on the number.
具体的には、Ｒ11〜Ｒ15、Ｒ21〜Ｒ25が上記（ｉ）のアルミニウム錯体（錯体３ａ）と、Ｒ11〜Ｒ15、Ｒ21〜Ｒ25が上記（v）のアルミニウム錯体（錯体５）の発光挙動を比較すると、最大吸収波長はそれぞれ３５３及び３３２ｎｍであり、発光帯ピークはそれぞれ４２０及び４１１ｎｍである。このように、本発明のアルミニウム錯体では、ジベンゾイルメタニド配位子におけるフッ素の置換位置及び数を選択することにより発光波長の微調整をすることが可能である。 Specifically, R 11 to R 15 and R 21 to R 25 are the aluminum complex (complex 3a) of the above (i), and R 11 to R 15 and R 21 to R 25 are the aluminum complex of the above (v) ( Comparing the emission behavior of the complex 5), the maximum absorption wavelengths are 353 and 332 nm, respectively, and the emission band peaks are 420 and 411 nm, respectively. As described above, in the aluminum complex of the present invention, the emission wavelength can be finely adjusted by selecting the substitution position and number of fluorine in the dibenzoylmethanide ligand.
以下、実施例を挙げて本発明を説明するが、本発明は下記の例に限定されるものではない。
なお、実施例のアルミニウム錯体について、ＮＭＲは、ブルカー株式会社製のＡＶＡＮＣＥ−III４００を使用し、ＳＩ−ＭＳは日立株式会社製のＭ−２５００を使用し、元素分析はパーキンエルマー株式会社製のＰＥ−２４００を使用して測定した。
また、電子吸収スペクトル及び発光スペクトルは日本分光株式会社製のＪＡＳＣＯ−Ｖ−６６０及びＦＰ−６５００を使用して測定した。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to the following example.
In addition, about the aluminum complex of an Example, NMR uses AVANCE-III400 made from Bruker, SI-MS uses M-2500 made from Hitachi, and elemental analysis is PE made from Perkin Elmer Co., Ltd. -2400.
Moreover, the electronic absorption spectrum and the emission spectrum were measured using JASCO-V-660 and FP-6500 manufactured by JASCO Corporation.
実施例１：アルミニウム錯体３ａ
窒素雰囲気下、３００ｍｌの反応容器に塩化アルミニウム（0.026 mol）のテトラクロロエタン溶液（２０ｍｌ）を入れ、４５℃に温めた後、３，５−ジフルオロベンゾイルクロリド（0.026 mol）を加えた。室温まで冷却後、酢酸ビニル（0.026 mol）をゆっくりと加え、その後、３５℃で１０時間撹拌した。反応混合物を１０％希塩酸溶液に移し、水蒸気蒸留により溶媒を除去した。残留物をジエチルエーテルで抽出し、シリカゲルカラムで精製し、無色の結晶（収率５５％）を得た。ＴＬＣ（薄層クロマトグラフィ）、ＮＭＲ及びＳＩ−ＭＳ分析より原料となる対応するフッ素置換配位子の生成を確認した。得られた配位子（3.7 mmol）を１５ｍｌの反応溶液に加え、メタノール（１５ｍｌ）を加えて溶かした後、ナトリウムメトキシド（3.7 mmol）のメタノール溶液（５ｍｌ）及び塩化アルミニウム（1.2 mmol）のメタノール溶液（１０ｍｌ）を加えて、２時間室温で撹拌した。反応混合物の溶媒を濃縮除去し、クロロホルムで抽出し、カラムクロマトグラフィーで精製し、黄色の結晶（収率８５％）を得た。
1H NMR (400 MHz, CDCl3, TMS(内部標準物質)): δ7.50-7.45 (m, 12H, PhH), 7.00-6.93 (m, 6H, PhH), 6.78 (s, 3H). SI-MS: 617 (M-3a) m/z. IR (KBr disk, cm-1): 1564, 1543, 1524, 1458, 1387, 1348, 1315, 1125, 990, 789. 元素分析: Calcd for C45H21AlF12O6 (%): C 59.22, H 2.32; found: C 59.10, H 2.11.
アセトニトリル溶液として測定した電子吸収スペクトルは３５３ｎｍに最大吸収を示し（図１）、３５３ｎｍで励起したところ４２０ｎｍ付近にピークを有する発光帯を示した（図６）。
Example 1: Aluminum complex 3a
Under a nitrogen atmosphere, a tetrachloroethane solution (20 ml) of aluminum chloride (0.026 mol) was placed in a 300 ml reaction vessel, warmed to 45 ° C., and 3,5-difluorobenzoyl chloride (0.026 mol) was added. After cooling to room temperature, vinyl acetate (0.026 mol) was slowly added, and then stirred at 35 ° C. for 10 hours. The reaction mixture was transferred to a 10% dilute hydrochloric acid solution and the solvent was removed by steam distillation. The residue was extracted with diethyl ether and purified with a silica gel column to obtain colorless crystals (yield 55%). The production | generation of the corresponding fluorine substitution ligand used as a raw material was confirmed from TLC (thin layer chromatography), NMR, and SI-MS analysis. The obtained ligand (3.7 mmol) was added to 15 ml of the reaction solution, methanol (15 ml) was added and dissolved, and then a solution of sodium methoxide (3.7 mmol) in methanol (5 ml) and aluminum chloride (1.2 mmol). Methanol solution (10 ml) was added and stirred at room temperature for 2 hours. The solvent of the reaction mixture was concentrated and removed, extracted with chloroform, and purified by column chromatography to obtain yellow crystals (yield 85%).
1 H NMR (400 MHz, CDCl 3 , TMS (internal standard)): δ7.50-7.45 (m, 12H, PhH), 7.00-6.93 (m, 6H, PhH), 6.78 (s, 3H). SI -MS: 617 (M-3a) m / z.IR (KBr disk, cm -1 ): 1564, 1543, 1524, 1458, 1387, 1348, 1315, 1125, 990, 789. Elemental analysis: Calcd for C 45 H 21 AlF 12 O 6 (%): C 59.22, H 2.32; found: C 59.10, H 2.11.
The electron absorption spectrum measured as an acetonitrile solution showed a maximum absorption at 353 nm (FIG. 1) and an emission band having a peak near 420 nm when excited at 353 nm (FIG. 6).
実施例２： アルミニウム錯体３ｂ
３，５−ジフルオロベンゾイルクロリドの代わりに、２，６−ジフルオロベンゾイルクロリドを用いた以外は、実施例１と同様の方法でそれぞれ配位子である無色の結晶（収率８０％）及びアルミニウム錯体の無色の結晶（収率９１％）を得た。ＴＬＣ、ＮＭＲ及びＳＩ−ＭＳ分析よりアルミニウム錯体３bの生成を確認した。
1H NMR (400 MHz, CDCl3, TMS(内部標準物質)): δ7.28 (t, J = 8.4 Hz, 6H, PhH), δ6.86 (t, J = 8.4 Hz, 12H, PhH),6.32 (s, 3H, CH). SI-MS: 617 (M-3b) m/z. IR (KBr disk, cm-1): 1626, 1597, 1560, 1525, 1473, 1423, 1389, 1315, 1003. 元素分析: Calcd for C45H21AlF12O6 (%): C 59.22, H 2.32; found: C 59.01, H 2.22.
アセトニトリル溶液として測定した電子吸収スペクトルは３２９ｎｍに最大吸収を示し（図２）、３２９ｎｍで励起したところ４２３ｎｍ付近にピークを有する発光帯を示した（図７）。
Example 2: Aluminum complex 3b
Colorless crystals (yield 80%) and an aluminum complex as ligands in the same manner as in Example 1 except that 2,6-difluorobenzoyl chloride was used instead of 3,5-difluorobenzoyl chloride. Of colorless crystals (yield 91%) was obtained. Formation of aluminum complex 3b was confirmed by TLC, NMR and SI-MS analysis.
1 H NMR (400 MHz, CDCl 3 , TMS (internal standard)): δ7.28 (t, J = 8.4 Hz, 6H, PhH), δ6.86 (t, J = 8.4 Hz, 12H, PhH), 6.32 (s, 3H, CH) .SI-MS: 617 (M-3b) m / z.IR (KBr disk, cm -1 ): 1626, 1597, 1560, 1525, 1473, 1423, 1389, 1315, 1003 Elemental analysis: Calcd for C 45 H 21 AlF 12 O 6 (%): C 59.22, H 2.32; found: C 59.01, H 2.22.
The electron absorption spectrum measured as an acetonitrile solution showed maximum absorption at 329 nm (FIG. 2), and when excited at 329 nm, showed an emission band having a peak near 423 nm (FIG. 7).
実施例３：アルミニウム錯体４ａ
３，５−ジフルオロベンゾイルクロリドの代わりに、２，４，６−トリフルオロベンゾイルクロリドを用いた以外は、実施例１と同様の方法でそれぞれ配位子である無色の結晶（収率６２％）及びアルミニウム錯体無色の結晶（収率９５％）を得た。ＴＬＣ、ＮＭＲ及びＳＩ−ＭＳ分析よりアルミニウム錯体４ａの生成を確認した。
1H NMR (400 MHz, CDCl3, TMS(内部標準物質)): δ6.64 (t, J = 8.4 Hz, 12H, PhH), 6.224 (s, 3H, CH). SI-MS: 689 (M-4a) m/z. IR (KBr disk, cm-1): 1640, 1607, 1568, 1528, 1458, 1408, 1387, 1348, 1123, 1080, 1036, 1001, 843. 元素分析: Calcd for C45H15AlF18O6 (%): C 52.96, H 1.48; found: C 52.82, H 1.37.
アセトニトリル溶液として測定した電子吸収スペクトルは３３１ｎｍに最大吸収を示し（図３）、３３１ｎｍで励起したところ４０５ｎｍ付近にピークを有する発光帯を示した（図８）。
Example 3: Aluminum complex 4a
Colorless crystals as ligands (62% yield) respectively in the same manner as in Example 1 except that 2,4,6-trifluorobenzoyl chloride was used instead of 3,5-difluorobenzoyl chloride. And an aluminum complex colorless crystal (yield 95%) was obtained. The formation of aluminum complex 4a was confirmed by TLC, NMR and SI-MS analysis.
1 H NMR (400 MHz, CDCl 3 , TMS (internal standard)): δ6.64 (t, J = 8.4 Hz, 12H, PhH), 6.224 (s, 3H, CH) .SI-MS: 689 (M -4a) m / z. IR (KBr disk, cm -1 ): 1640, 1607, 1568, 1528, 1458, 1408, 1387, 1348, 1123, 1080, 1036, 1001, 843. Elemental analysis: Calcd for C 45 H 15 AlF 18 O 6 (%): C 52.96, H 1.48; found: C 52.82, H 1.37.
The electron absorption spectrum measured as an acetonitrile solution showed a maximum absorption at 331 nm (FIG. 3) and an emission band having a peak near 405 nm when excited at 331 nm (FIG. 8).
実施例４：アルミニウム錯体４ｂ
３，５−ジフルオロベンゾイルクロリドの代わりに、３，４，５−トリフルオロベンゾイルクロリドを用いた以外は、実施例１と同様の方法でそれぞれ配位子である無色の結晶（収率５０％）及びアルミニウム錯体の黄色の結晶（収率６１％）を得た。ＴＬＣ、ＮＭＲ及びＳＩ−ＭＳ分析よりアルミニウム錯体４ｂの生成を確認した。
1H NMR (400 MHz, CDCl3, TMS(内部標準物質)): δ7.60 (t, J = 7.4 Hz, 12H, PhH), 6.70 (s, 3H, CH). SI-MS: 690 (M-4b) m/z. IR (KBr disk, cm-1): 1568, 1497, 1462, 1371, 1343, 1230, 1047, 787, 621. 元素分析: Calcd for C45H15AlF18O6 (%): C 52.96, H 1.48; found: C 53.00, H 1.22.
アセトニトリル溶液として測定した電子吸収スペクトルは３５２ｎｍに最大吸収を示し（図４）、３５２ｎｍで励起したところ４１７ｎｍ付近にピークを有する発光帯を示した（図９）。
Example 4: Aluminum complex 4b
Colorless crystals as ligands (50% yield) in the same manner as in Example 1 except that 3,4,5-trifluorobenzoyl chloride was used instead of 3,5-difluorobenzoyl chloride. And yellow crystals of aluminum complex (61% yield) were obtained. Formation of aluminum complex 4b was confirmed by TLC, NMR and SI-MS analysis.
1 H NMR (400 MHz, CDCl 3 , TMS (internal standard)): δ7.60 (t, J = 7.4 Hz, 12H, PhH), 6.70 (s, 3H, CH). SI-MS: 690 (M -4b) m / z.IR (KBr disk, cm -1 ): 1568, 1497, 1462, 1371, 1343, 1230, 1047, 787, 621.Elemental analysis: Calcd for C 45 H 15 AlF 18 O 6 (% ): C 52.96, H 1.48; found: C 53.00, H 1.22.
The electron absorption spectrum measured as an acetonitrile solution showed maximum absorption at 352 nm (FIG. 4), and when excited at 352 nm, showed an emission band having a peak near 417 nm (FIG. 9).
実施例５：アルミニウム錯体５
３，５−ジフルオロベンゾイルクロリドの代わりに、２，３，５，６−テトラフルオロベンゾイルクロリドを用いた場合は一段階でアルミニウム錯体が生成した。窒素雰囲気下、３００ｍｌの反応容器に塩化アルミニウム（0.026 mmol）のテトラクロロエタン溶液（２０ｍｌ）を入れ、４５℃に温めた後、２，３，５，６−ジフルオロベンゾイルクロリド（0.026 mmol）を加えた。室温まで冷却後、酢酸ビニル（0.026 mmol）をゆっくりと加え、その後、３５℃で１０時間撹拌した。反応混合物を１０％希塩酸溶液に移し、水蒸気蒸留により溶媒を除去した。残留物をジエチルエーテルで抽出し、シリカゲルカラムで精製し、目的のアルミニウム錯体の無色の結晶（収率６６％）を得た。ＴＬＣ（薄層クロマトグラフィ）、ＮＭＲ及びＳＩ−ＭＳ分析よりアルミニウム錯体の生成を確認した。
1H NMR (400 MHz, CDCl3, TMS(内部標準物質)): δ7.18-7.10 (m, 6H, PhH), 6.34 (s, 1H, CH) (s). SI-MS: 761 (M-5) m/z. IR (KBr disk, cm-1): 1587, 1528, 1506, 1435, 1383, 1319, 1277, 1179, 1001, 941, 635. 元素分析: Calcd for C45H9AlF24O6 (%): C 47.89, H 0.80; found: C 47.68, H 1.06。
アセトニトリル溶液として測定した電子吸収スペクトルは３３２ｎｍに最大吸収を示し（図５）、３３２ｎｍで励起したところ４１１ｎｍ付近にピークを有する発光帯を示した（図１０）。
Example 5: Aluminum complex 5
When 2,3,5,6-tetrafluorobenzoyl chloride was used instead of 3,5-difluorobenzoyl chloride, an aluminum complex was formed in one step. Under a nitrogen atmosphere, a 300 ml reaction vessel was charged with a solution of aluminum chloride (0.026 mmol) in tetrachloroethane (20 ml), warmed to 45 ° C., and 2,3,5,6-difluorobenzoyl chloride (0.026 mmol) was added. . After cooling to room temperature, vinyl acetate (0.026 mmol) was slowly added and then stirred at 35 ° C. for 10 hours. The reaction mixture was transferred to a 10% dilute hydrochloric acid solution and the solvent was removed by steam distillation. The residue was extracted with diethyl ether and purified with a silica gel column to obtain colorless crystals of the target aluminum complex (yield 66%). Formation of an aluminum complex was confirmed by TLC (thin layer chromatography), NMR and SI-MS analysis.
1 H NMR (400 MHz, CDCl 3 , TMS (internal standard)): δ7.18-7.10 (m, 6H, PhH), 6.34 (s, 1H, CH) (s). SI-MS: 761 (M -5) m / z. IR (KBr disk, cm -1 ): 1587, 1528, 1506, 1435, 1383, 1319, 1277, 1179, 1001, 941, 635. Elemental analysis: Calcd for C 45 H 9 AlF 24 O 6 (%): C 47.89, H 0.80; found: C 47.68, H 1.06.
The electron absorption spectrum measured as an acetonitrile solution showed a maximum absorption at 332 nm (FIG. 5) and an emission band having a peak near 411 nm when excited at 332 nm (FIG. 10).
本発明の発光特性を有するフッ素置換ジベンゾイルメタニドを配位子とするアルミニウム錯体は、配位子のフッ素置換の位置または数を選択することにより、発光波長の微調整をすることができ、ＥＬ素子を指向した発光材料として有用である。 The aluminum complex having a fluorine-substituted dibenzoylmethanide having a luminescent property of the present invention as a ligand can finely adjust the emission wavelength by selecting the position or number of fluorine substitution of the ligand, It is useful as a light emitting material directed to an EL element.
Claims (2)
で示されるアルミニウム錯体。 Formula (I)
An aluminum complex represented by
で示されるアルミニウム錯体。
Formula (I)
An aluminum complex represented by
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