CN108467412A - 一种黄绿光苯基吡啶铱配合物及其制备方法和应用 - Google Patents
一种黄绿光苯基吡啶铱配合物及其制备方法和应用 Download PDFInfo
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- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 21
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 (trifluoromethyl) phenyl Chemical group 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005401 electroluminescence Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 claims abstract description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 150000003222 pyridines Chemical class 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract 4
- 235000019253 formic acid Nutrition 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000539 dimer Substances 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- LSZMVESSGLHDJE-UHFFFAOYSA-N 2-bromo-4-methylpyridine Chemical class CC1=CC=NC(Br)=C1 LSZMVESSGLHDJE-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical class OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 claims description 2
- KZAQTVQJVOALDK-UHFFFAOYSA-N 5-(trifluoromethyl)-1h-1,2,4-triazole Chemical compound FC(F)(F)C=1N=CNN=1 KZAQTVQJVOALDK-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 abstract 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004984 proton decoupled 19F NMR spectroscopy Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
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- 238000000295 emission spectrum Methods 0.000 description 2
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- PLVCYMZAEQRYHJ-UHFFFAOYSA-N (2-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Br PLVCYMZAEQRYHJ-UHFFFAOYSA-N 0.000 description 1
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical class CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- 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
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Abstract
本发明涉及一种黄绿光苯基吡啶铱配合物,该配合物具有如下结构式其中,R1可独立的为甲基、乙基、叔丁基或异丙基等,R2可独立的为3,5‑二(三氟甲基)苯基、3,5‑二氟苯基、苯基、4‑氟苯基或4‑三氟甲基苯基,辅助配体可独立的为2‑(3‑(三氟甲基)‑1H‑1,2,4‑三唑‑5‑基)吡啶、吡啶‑2‑甲酸、乙酰丙酮。发明黄绿光铱(III)配合物具有溶解性好,黄绿光发射等特性,可以用作电致发光磷光材料应用于湿法有机电致发光器件。
Description
技术领域
本发明涉及一种黄绿光苯基吡啶铱配合物,尤其涉及一种可湿法制备电致发光二极管的黄绿光铱配合物及其该配合物的制备方法和应用。
技术背景
磷光过渡金属配合物的设计与合成在近年来取得的长足的进步,它可以被用于有机发光二极管(OLEDs),而OLEDs在未来的显示及固态发光技术中有潜在的使用价值。相比液晶显示技术,OLEDs优势明显,它更薄,更轻;制造工艺简单,成本低;主动发光,无需背景光源,能耗低;全固态结构,抗震效果好,环境适应性强;可弯曲折叠;无观察视角限制;更清晰。而相比荧光发射,磷光过渡金属配合物利用单线态和三线态激子能极大地提高器件效率。
目前报道的可用于湿法制备的黄绿光波段的铱(III)配合物通常都是通过增加配体的共轭程度来实现黄绿光的发射,但是增加配体的共轭程度会降低配合物的溶剂性,不利于实现器件的湿法制备,同时还会降低配合物发光量子效率,有必要开发一类具有较小共轭结构且具有优异溶解性的黄绿光铱(III)配合物,本发明正是提供了一类可湿法制备电致发光二极管的黄绿光铱(III)配合物。
发明内容
本发明的目的是提供一类可湿法制备电致发光二极管的黄绿光铱(III)配合物,该配合物具有溶解性好,黄绿光发射的特性。
为了实现上述目的,本发明所采取的技术方案为:一种黄绿光苯基吡啶铱配合物,该配合物具有如下结构式
其中,R1可独立的为烷烃基,R2可独立的为3,5-二(三氟甲基)苯基、3,5-二氟苯基、苯基、4-氟苯基或4-三氟甲基苯基,辅助配体可独立的为2-(3-(三氟甲基)-1H-1,2,4-三唑-5-基)吡啶、吡啶-2-甲酸、乙酰丙酮。
进一步的,R1为甲基、乙基、叔丁基、异丙基中的一种,R2为3,5-二(三氟甲基)苯基、3,5-二氟苯基、苯基、4-氟苯基、4-三氟甲基苯基中的一种,辅助配体为2-(3-(三氟甲基)-1H-1,2,4-三唑-5-基)吡啶、吡啶-2-甲酸、乙酰丙酮中的一种。
本发明还提供了一种黄绿光苯基吡啶铱配合物的制备方法,包括以下步骤
步骤1,在惰性气体条件下、烷氧基乙醇溶剂体系中,将多取代苯基吡啶与三水合三氯化铱按摩尔比2.2:1在110℃反应,得到铱氯桥二聚体;
步骤2,在烷氧基乙醇溶剂体系中,无水碳酸钠存在下,将铱氯桥二聚体与辅助配体反应,得到黄绿光铱配合物;
所述无水碳酸钠的摩尔量为辅助配体摩尔量的5-10倍;
所述取代苯基吡啶结构式为:
进一步的,所述烷氧基乙醇溶剂体系为2-甲氧基乙醇或2-乙氧基乙醇与水组成的混合溶剂,其中2-甲氧基乙醇或2-乙氧基乙醇与水的体积比为3:1。
进一步的,加入所述铱氯桥二聚体与辅助配体摩尔比为1:1.1~1.5。
进一步的,加入所述取代苯基吡啶与三水合三氯化铱摩尔比为2.0~2.3:1。
进一步的,所述取代苯基吡啶为2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶,所述取代苯基吡啶的制备步骤为:
a取2-溴-4-甲基吡啶、4-溴苯硼酸、四(三苯基膦)钯、饱和碳酸钾水溶液,无水甲醇,甲苯,加入到带搅拌子的单口反应瓶中,通氮气,回流反应,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离得到产物2-(4-溴苯基)-4-甲基吡啶,
b取2-(4-溴苯基)-4-甲基吡啶、3,5-二(三氟甲基)苯硼酸、四(三苯基膦)钯、饱和碳酸钠水溶液、无水甲醇、甲苯,加入到带搅拌子的单口反应瓶中,通氮气,回流反应,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离制得。
所述的黄绿光苯基吡啶铱配合物作为有机电致磷光发光材料的应用。
本发明还提供了一种有机电致发光器件,包括第一电极、第二电极,以及在第一电极与第二电极之间形成的一层或多层有机功能层,至少一层有机功能层中包含有权利要求1所述的黄绿光苯基吡啶铱配合物。
本发明所产生的有益效果包括:
本发明黄绿光铱(III)配合物具有溶解性好,黄绿光发射等特性,可以用作电致发光磷光材料应用于湿法有机电致发光器件。
附图说明
图1 2-(4-溴苯基)-4-甲基吡啶核磁共振氢谱;
图2 2-(4-溴苯基)-4-甲基吡啶核磁共振碳谱;
图3 2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶核磁共振氢谱;
图4 2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶核磁共振碳谱;
图5 2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶核磁共振氟谱;
图6 Ir1核磁共振氢谱;
图7 Ir1核磁共振氟谱;
图8 Ir1质谱;
图9 Ir2核磁共振氢谱;
图10 Ir2核磁共振氟谱;
图11 Ir2质谱;
图12 Ir1在二氯甲烷中发射光谱;
图13 Ir2在二氯甲烷中发射光谱;
图14 Ir1电致发光光谱;
图15基于Ir1器件的电流效率-亮度曲线;
图16基于Ir1器件的功率效率-亮度曲线。
具体实施方式
下面结合具体实施例对本发明做进一步详细的解释说明,但下述实施例并不是用于限定本发明的实施范围,凡是依据本发明技术内容所做的等效变化与润饰,均应包含在本发明的技术范畴之内。
实施例1:配合物Ir1的合成
配合物Ir1即
合成反应式如下:
合成步骤为:
(1)2-(4-溴苯基)-4-甲基吡啶的合成
取2-溴-4-甲基吡啶1.45g,4-溴苯硼酸1.7g,四(三苯基膦)钯0.32g,15mL饱和碳酸钾水溶液,10mL无水甲醇,40mL甲苯,依次加入到带搅拌子的单口反应瓶中,通氮气,回流反应15h后,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离得到产物,产率80%。2-(4-溴苯基)-4-甲基吡啶核磁共振氢谱和核磁共振碳谱分别见图1和图2,1H NMR(400MHz,CDCl3,δ):8.56(d,J=4.80Hz,1H),7.90-7.87(m,2H),7.63-7.59(m,2H),7.54(s,1H),7.10(d,J=4.40Hz,1H),2.44(s,3H).13C{1H}NMR(100MHz,CDCl3,δ):156.13,149.54,147.95,138.41,131.82,128.50,123.48,123.28,121.28,21.26。
(2)2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶的合成
取2-(4-溴苯基)-4-甲基吡啶1.45g,3,5-二(三氟甲基)苯硼酸1.09g,四(三苯基膦)钯0.16g,15mL饱和碳酸钠水溶液,10mL无水甲醇,40mL甲苯,依次加入到带搅拌子的单口反应瓶中,通氮气,回流反应15h后,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离得到产物,产率85%。2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶核磁共振氢谱、核磁共振碳谱和核磁共振氟谱分别见图3、图4和图5,1H NMR(400MHz,CDCl3,δ):8.61(dd,J=0.40Hz,J=4.80Hz,1H),8.18-8.14(m,2H),8.09(s,2H),7.64(sep,J=0.80Hz,1H),7.13(ddd,J=0.80Hz,J=1.60Hz,J=5.20Hz,1H),2.47(s,3H).13C{1H}NMR(100MHz,CDCl3,δ):156.18,149.54,147.93,142.74,140.00,138.28,132.16(q,J=33.00Hz),127.73,127.43,127.04(q,J=2.70Hz),124.41(q,J=271.10Hz),123.56,121.49,120.99,127.04(sep,J=3.80Hz),21.14.19F{1H}NMR(376MHz,CDCl3,δ):-62.79(s).
(3)铱氯桥二聚体的合成
取2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶0.48g,三水合三氯化铱0.20g,2-乙氧基乙醇12mL,去离子水4mL,依次加入带搅拌子的单口反应瓶中,通氮气,加热至110℃回流搅拌反应24h后,自然冷却到室温,向反应液中倒入40mL去离子水,析出大量深棕色絮状固体,抽滤水洗,40℃真空干燥,得2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶合铱氯桥二聚体黄色固体。
(4)配合物Ir1的合成
将干燥得到的400mg的2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶合铱氯桥二聚体加入含有20mL 2-乙氧基乙醇的100mL单口反应瓶,加入2-(3-(三氟甲基)-1H-1,2,4-三唑-5-基)吡啶130mg,碳酸钠粉末215mg,通氮气,100℃下反应12h后抽滤得到滤液,柱层析下分离,洗脱剂为二氯甲烷得到黄绿色固体产物0.37g。该配合物在二氯甲烷溶液中发射波长为525nm,半峰宽72nm,如图12所示。Ir1核磁共振氢谱、核磁共振氟谱和质谱分别为图6、图7和图8,可得,1H NMR(400MHz,CDCl3,δ):8.35(d,J=8.00Hz,1H),7.90(dt,J=1.60Hz,J=8.00Hz,1H),7.86(d,J=5.60Hz,1H),7.80(s,1H),7.77-7.71(m,10H),7.41(d,J=5.60Hz,1H),7.30(dd,J=2.00Hz,J=7.20Hz,1H),7.23-7.20(m,2H),6.93(dd,J=1.20Hz,J=6.00Hz,1H),6.82(dd,J=1.20Hz,J=5.60Hz,1H),6.50(d,J=1.60Hz,1H),6.43(d,J=2.00Hz,1H),2.55(s,3H),2.54(s,3H).19F{1H}NMR(376MHz,CDCl3,δ):-62.98(s),-63.01(s),-63.17(s).MALDI-TOF-MS(m/z):calcd for C48H28F15IrN6,1165.97;found,1166.03.
实施例2:配合物Ir2的合成
配合物Ir2即
合成过程如下:
将400mg的2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶合铱氯桥二聚体加入含有20mL2-乙氧基乙醇的100mL单口反应瓶,加入吡啶-2-甲酸75mg,碳酸钠粉末215mg,通氮气,100℃下反应12h后抽滤得到滤液,柱层析下分离,洗脱剂为二氯甲烷得到黄绿色固体产物0.30g。该配合物在二氯甲烷溶液中发射波长为535nm,半峰宽75nm,如图13所示。Ir2核磁共振氢谱、核磁共振氟谱和质谱分别为图9、图10和图11,1H NMR(400MHz,CDCl3,δ):8.75(d,J=5.60Hz,1H),8.39(d,J=7.60Hz,1H),7.95(t,J=7.60Hz,1H),7.89(d,J=5.20Hz,1H),7.81-7.68(m,10H),7.44-7.40(m,2H),7.22(d,J=7.60Hz,1H),7.16(d,J=8.40Hz,1H),7.16(d,J=8.40Hz,1H),7.12(d,J=5.60Hz,1H),6.88(d,J=5.60Hz,1H),6.57(s,1H),6.34(s,1H),2.59(s,6H).19F{1H}NMR(376MHz,CDCl3,δ):-63.00(s),-63.01(s).MALDI-TOF-MS(m/z):calcd for C46H28F12IrN3O2,1075.16;found,1075.14.
实施例3
使用实施例1制备的配合物Ir1掺杂在m-MTDATA和26Dczppy混合主体材料中制造有机电致发光器件。首先,在涂覆有ITO的玻璃表面旋涂30nm的PEDOT:PSS作为空穴注入层;然后,在空穴注入层上旋涂掺杂4%、6%和10%Ir1的m-MTDATA和26Dczppy混合主体形成40nm的发光层;随后,依次沉积60nm的电子传输层TmPyPb、0.8nm的界面层LiF和100nm阴极铝。
测试器件的电致发光光谱如图14所示,发射峰位于528nm,色坐标CIE值X=0.37,Y=0.60。器件的电流密度-电压-亮度曲线如图13所示,具有较好的整流特性,最大亮度为11453cd/m2。器件的电流效率-电流密度-功率效率如图15和16所示,最大电流效率和功率效率分别为9.54cd/A和4.13lm/W。
上述仅为本发明的优选实施例,本发明并不仅限于实施例的内容。对于本领域中的技术人员来说,在本发明的技术方案范围内可以有各种变化和更改,所作的任何变化和更改,均在本发明保护范围之内。
Claims (9)
1.一种黄绿光苯基吡啶铱配合物,其特征在于:该配合物具有如下结构式
其中,R1为烷烃基,R2为3,5-二(三氟甲基)苯基、3,5-二氟苯基、苯基、4-氟苯基、4-三氟甲基苯基中的一种,辅助配体为2-(3-(三氟甲基)-1H-1,2,4-三唑-5-基)吡啶、吡啶-2-甲酸、乙酰丙酮中的一种。
2.根据权利要求1所述的黄绿光苯基吡啶铱配合物,其特征在于:R1为甲基、乙基、叔丁基、异丙基中的一种。
3.一种权利要求1所述的黄绿光苯基吡啶铱配合物的制备方法,其特征在于:包括以下步骤
步骤1,在惰性气体条件下、烷氧基乙醇溶剂体系中,将多取代苯基吡啶与三水合三氯化铱按摩尔比2.2:1在110℃反应,得到铱氯桥二聚体;
步骤2,在烷氧基乙醇溶剂体系中,无水碳酸钠存在下,将铱氯桥二聚体与辅助配体反应,得到黄绿光铱配合物;
所述无水碳酸钠的摩尔量为辅助配体摩尔量的5-10倍;
所述取代苯基吡啶结构式为:
4.根据权利要求3所述的黄绿光苯基吡啶铱配合物的制备方法,其特征在于:所述烷氧基乙醇溶剂体系为2-甲氧基乙醇或2-乙氧基乙醇与水组成的混合溶剂,其中2-甲氧基乙醇或2-乙氧基乙醇与水的体积比为3:1。
5.根据权利要求3所述的黄绿光苯基吡啶铱配合物的制备方法,其特征在于:加入所述铱氯桥二聚体与辅助配体摩尔比为1:1.1~1.5。
6.根据权利要求3所述的黄绿光苯基吡啶铱配合物的制备方法,其特征在于:加入所述取代苯基吡啶与三水合三氯化铱摩尔比为2.0~2.3:1。
7.根据权利要求3所述的黄绿光苯基吡啶铱配合物的制备方法,其特征在于:所述取代苯基吡啶为2-(3',5'-二(三氟甲基)-[1,1'-二苯基]-4-基)-4-甲基吡啶,所述取代苯基吡啶的制备步骤为:
a取2-溴-4-甲基吡啶、4-溴苯硼酸、四(三苯基膦)钯、饱和碳酸钾水溶液,无水甲醇,甲苯,加入到带搅拌子的单口反应瓶中,通氮气,回流反应,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离得到产物2-(4-溴苯基)-4-甲基吡啶,
b取2-(4-溴苯基)-4-甲基吡啶、3,5-二(三氟甲基)苯硼酸、四(三苯基膦)钯、饱和碳酸钠水溶液、无水甲醇、甲苯,加入到带搅拌子的单口反应瓶中,通氮气,回流反应,旋出多余的甲苯,加二氯甲烷和水萃取出反应物,柱层析下分离制得。
8.权利要求1所述的黄绿光苯基吡啶铱配合物作为有机电致磷光发光材料的应用。
9.一种有机电致发光器件,包括第一电极、第二电极,以及在第一电极与第二电极之间形成的一层或多层有机功能层,其特征在于:至少一层有机功能层中包含有权利要求1所述的黄绿光苯基吡啶铱配合物。
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