CN105576138A - 基于铂(ii)异喹啉-吡啶-苯的络合物、其制备方法和由其制成的有机发光二极管 - Google Patents
基于铂(ii)异喹啉-吡啶-苯的络合物、其制备方法和由其制成的有机发光二极管 Download PDFInfo
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- CN105576138A CN105576138A CN201510893536.5A CN201510893536A CN105576138A CN 105576138 A CN105576138 A CN 105576138A CN 201510893536 A CN201510893536 A CN 201510893536A CN 105576138 A CN105576138 A CN 105576138A
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- 238000000034 method Methods 0.000 title claims abstract description 12
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 23
- -1 sulfo- Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004442 acylamino group Chemical group 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
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- 125000005504 styryl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
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- 229910052711 selenium Inorganic materials 0.000 claims description 4
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 235000012736 patent blue V Nutrition 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
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- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims 1
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- 125000002524 organometallic group Chemical group 0.000 abstract 2
- OCLVYABFYBYSBA-UHFFFAOYSA-N benzene;isoquinoline;pyridine Chemical compound C1=CC=CC=C1.C1=CC=NC=C1.C1=NC=CC2=CC=CC=C21 OCLVYABFYBYSBA-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 45
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- 238000003786 synthesis reaction Methods 0.000 description 15
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- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 13
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- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical compound [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZMCQQCBOZIGNRV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(1,2,4-triazol-1-yl)ethyl]benzamide Chemical compound NCC1=CC(OC2=CC=CC(=C2)C(=O)NCCN2C=NC=N2)=NC(=C1)C(F)(F)F ZMCQQCBOZIGNRV-UHFFFAOYSA-N 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
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- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 3
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 3
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 150000003513 tertiary aromatic amines Chemical class 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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Abstract
包含三齿异喹啉-吡啶-苯-基配体、单齿配体和铂(II)中心的有机金属络合物表现出高发光量子效率和良好的热稳定性。还描述了由有机金属络合物制成的有机发光二极管。
Description
本申请是申请号为201080036152.7母案的分案申请。该母案的申请日为2010年5月18日;发明名称为“基于铂(II)异喹啉-吡啶-苯的络合物、其制备方法和由其制成的有机发光二极管”。
技术领域
本发明涉及新型铂(II)络合物及其在有机发光二极管(OLED)中的用途。本发明中的铂(II)络合物具有高发光量子效率和良好的热稳定性。可以制造高效率单色和白色OLED(WOLED)。
背景技术
最初在上世纪六十年代观察和研究了有机电致发光(美国专利No. 3,172,862)。在八十年代,Tang公开了双层结构OLED(有机发光器件)(美国专利No. 4,356,429;Appl. Phvs. Lett. 1987, 51, 12, 913)。这种发现基于使用包括发光电子传输层(emissiveelectron-transporting layer)和合适的有机材料的空穴传输层的多层结构。选择Alq3(q= 脱质子8-羟基喹啉基)作为发光电子传输材料。从那时起,持续研究OLED中使用的材料。OLED提供几个优点,包括:(1)低工作电压;(2)薄整体结构;(3)发射光而非调制光;(4)良好的发光效率;(5)全色潜力;和(6)高对比和分辨率。这些优点表明OLED可能用在平板显示器中。
对有机小分子进行研究以改进OLED的性能。通常,使用荧光和磷光材料作为OLED的发光层中的光发射体。来自荧光化合物的发光是由于在电致发光器件的发光层中形成单重态激子(singlet excitons)而发生的。美国公开专利申请No. 2003/178619 B2公开了在电致发光器件的发光层中在空穴和电子重组后产生理论上25%单重态激子和75%三重态激子(triplet exciton)。单重态激子将它们的能量转移给单重态激发态,而三重态激子将它们的能量转移给三重态激发态。大多数有机小分子表现出荧光;因此,只利用了生成的激子的25%,造成具有低热效率的器件。
Cambridge University的Friend等人在1990年在对聚(对苯乙炔)(poly(p-phenylene vinylene))(PPV)的电性质的研究过程中首次发现来自共轭聚合物的电致发光(Nature 1990, 347, 539)。在被两个电极之间的电流流激发时,观察到来自这种亮黄色聚合物的在551 nm处具有最大发射峰的黄绿色光。为解决溶解性问题,Heeger等人后来使用可溶PPV衍生物制造PLED(Appl. Phys. Lett. 1991, 1982)。
由于PLED可用于大面积平板显示器并相对便宜,其近年来已受到越来越多关注。早期通常通过旋涂制造PLED。但是,存在与这种旋涂相关的许多缺点,如溶液损耗和缺乏横向图案化能力,由此限制PLED的商业应用。为克服这些缺点,Yang等人已引入喷墨印刷(Appl. Phys. Lett. 1998, 2561),现在可以使用市售喷墨印刷机制造PLED。
近年来,发射红光、绿光和蓝光的聚合物积极用于制造全色板。但是,目前已知的聚合物,如聚(对亚苯基)(PPP)、PPV、聚噻吩(PT)和聚芴(PF)的商业应用受制于它们的氧化稳定性和/或结构和电子性质。尽管PPV基材料表现出高PL和EL效率且它们的发射能量可调,它们在并入EL器件中时通常发生光氧化降解(Anqew. Chem. Int. Ed. 1998, 37,403)。PPP的应用受其低溶解度限制。PF是发蓝光的材料,其表现出良好的热稳定性和高EL量子效率,但该聚合物中的链聚集和酮基缺陷位点会造成EL器件的劣化(J. Mater. Chem.2000, 10, 1471)。发光聚合物还在LED的制造中造成技术问题,包括颜色杂质、失衡的电荷注入和低EL效率。不同于荧光化合物,University of Southern California的Thompson等人和Princeton University的Forrest等人已联合报道了一系列具有不同颜色发射的有效磷光铱络合物(美国专利No. 6,515,298;J. Am. Chem. Soc. 2001, 123, 4304;Adv.Mat. 2001, 13, 1245)。Che等人也展示使用各种金属中心,如铂(II)、铜(I)、金(I)和锌(II)的有机金属络合物作为OLED发射体的用途(美国公开专利申请No. 2005/244672 A1;Chem. Eur. J. 2003, 9, 1263;Chem. Commun., 2002, 206;New J. Chem. 1999, 263;Appl. Phys. Lett., 1999, 74, 1361;Chem. Commun. 1998, 2101;Chem. Commun.1998, 2491)。
最近,在通过真空沉积法的高性能OLED的开发中表现出巨大成功的磷光金属-有机材料已附加到聚合物骨架上以制造新类型的发光聚合物,一些最近的实例是:Holdcroft等人的天蓝色光发射器件(Macromolecules 2006, 9157)和Cao等人的红光发射器件(Organometallics 2007, 26, 3699)。在2006年,Thompson及同事报道了最大外量子效率(EQE)为10.5%的高效率绿光发射PLED(Chem. Mater. 2006, 18, 386)。使用这种方法,已使用其上带有蓝光和红光发射单元的聚合物制造发射近白光(CIE: 0.30, 0.43)的PLED。由于PLED中所用的聚合材料具有高分子量并可溶于普通溶剂,它们是用于喷墨印刷的潜在候选物。
发明内容
本发明涉及具有结构I的化学结构的有机金属络合物的制备和在有机发光器件(OLED)中的用途:
结构I
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫基、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基;X是卤素、
其中A是碳、氮、氧、硅、磷、硫、砷和硒;B是连接R17和R19的化学键、
R6-R15独立地为氢、烷基、取代烷基、环烷基、芳基和取代芳基;R16-R23独立地为碳、氮、氧、硅、磷、硫、砷和硒;Z1-Z8独立地为氢、烷基、取代烷基、环烷基、芳基、取代芳基,且Z1-Z8可以与相邻基团形成5-7元环。本发明还提供可用于制造此类络合物的配体。
本发明进一步提供制造此类有机金属络合物的方法、包含其的OLED和制造此类OLED的方法。
本发明还提供可用于制造有机金属络合物的组合物、制造此类络合物的方法、包括此类络合物的OLED和制造此类OLED的方法。
对本申请而言,术语卤素、烷基、环烷基、芳基、酰基和烷氧基可具有下列含义:
本文所用的卤素或卤(halo)包括氟、氯、溴和碘,优选F、Cl、Br,特别优选F或Cl。
本文所用的芳基或芳基部分包括具有6至30个碳原子,优选6至18个碳原子的芳基,并由芳环或多个稠芳环构成。合适的芳基是例如,苯基、萘基、苊基、苊烯基(acenaphthylenyl)、蒽基、芴基、非那烯基(phenalenyl)、菲基。这种芳基可以是未取代(即所有能取代的碳原子都带有氢原子)或在该芳基的一个、多于一个或所有可取代位置上被取代。合适的取代基是例如卤素,优选F、Br或Cl,烷基,优选具有1至8个碳原子的烷基,特别优选甲基、乙基、异丙基或叔丁基,可以再次被取代或未取代的芳基,优选C6-芳基或芴基,杂芳基,优选含有至少一个氮原子的杂芳基,特别优选吡啶基,烯基,优选具有一个双键的烯基,特别优选具有双键和1至8个碳原子的烯基,或具有给体或受体作用的基团。对本发明的目的而言,具有给体作用的基团是表现出+1和/或+M作用的基团,具有受体作用的基团是表现出-1和/或-M作用的基团。合适的具有给体或受体作用的基团是卤素基团,优选F、Cl、Br,特别优选F,烷氧基、羰基、酯基团、胺基团、酰胺基团、CH2F基团、CHF2基团、CF3基团、CN基团、硫代基或SCN基团。芳基非常特别优选带有选自甲基、F、Cl和烷氧基的取代基,或芳基是未取代的。优选的是可任选被至少一个上述取代基取代的C6-芳基形式的芳基。该C6-芳基特别优选带有零个、一个或两个上述取代基,其中一个取代基优选位于相对于芳基的进一步连接点的对位,在两个取代基的情况下,这些各自位于相对于芳基的进一步连接点的间位。C6-芳基非常特别优选是未取代的苯基。本文所用的芳基或芳基部分优选是芴基或苯基,其可以未取代或被上述取代基,优选卤素、烷基或如本文所用的未取代或取代芴基所取代。
本文所用的烷基或烷基部分包括具有1至20个碳原子,优选1至10个碳原子,特别优选1至6个碳原子的烷基。这种烷基可以是支链或直链的,并可以被一个或多个杂原子,优选N、O或S插入。此外,这种烷基可以被关于芳基提到的一个或多个取代基取代。例如,可能的取代烷基包括三氟甲基。烷基也可以带有一个或多个芳基。所有提到的芳基都适合此目的。烷基特别优选选自甲基、乙基、异丙基、正丙基、异丁基、正丁基、叔丁基、仲丁基、异戊基、正戊基、仲戊基、新戊基、正己基、异己基和仲己基。非常特别优选的是甲基、异丙基和正己基。
本文所用的环烷基考虑了环状烷基基团(cyclic alkyl radicals)。优选的环烷基是含有3至7个碳原子的那些,并包括环丙基、环戊基、环己基等。另外,环烷基可任选被一个或多个选自卤素、CN、CO2R、C(O)R、NR2、环氨基、NO2和OR的取代基取代。
本文所用的酰基是用单键连接到CO基团上的如本文所用的烷基。
烷氧基是连接到氧上的如本文所用的烷基。
附图说明
通过审查联系附图作出的优选实施方案的下列详述,容易看出本发明的其它特征和优点,其中:
图1是有机发光二极管的构造的示意图;
图2是器件A的电流密度、电压和亮度(J-V-B)关系图;
图3是器件A的外量子效率、电流密度关系图;
图4是器件A的电致发光光谱;
图5是器件B的电流密度、电压和亮度(J-V-B)关系图;
图6是器件B的外量子效率、电流密度关系图;
图7是器件B的电致发光光谱;
图8是器件C的电流密度、电压和亮度(J-V-B)关系图;
图9是器件C的外量子效率、电流密度关系图;
图10是器件C的电致发光光谱;
图11是器件D的电流密度、电压和亮度(J-V-B)关系图;
图12是器件D的外量子效率、电流密度关系图;
图13是器件D的电致发光光谱;
图14是器件E的电流密度、电压和亮度(J-V-B)关系图;
图15是器件E的外量子效率、电流密度关系图;
图16是器件E的电致发光光谱;
图17是器件F的电流密度、电压和亮度(J-V-B)关系图;
图18是器件F的外量子效率、电流密度关系图;
图19是器件F的电致发光光谱;
图20是器件G的电流密度、电压和亮度(J-V-B)关系图;
图21是器件G的外量子效率、电流密度关系图;
图22是器件G的电致发光光谱;
图23是器件H的电流密度、电压和亮度(J-V-B)关系图;
图24是器件H的外量子效率、电流密度关系图;
图25是器件H的电致发光光谱;
图26是器件I的电流密度、电压和亮度(J-V-B)关系图;
图27是器件I的外量子效率、电流密度关系图;且
图28是器件I的电致发光光谱。
具体实施方式
具有结构I的化学结构的有机金属络合物被称作环金属化络合物。结构I中的铂中心(见上文)为+2氧化态并具有正方形平面几何形状。
该铂中心的配位点被一个三齿配体和一个单齿配体占据。三齿配体通过两个氮给体键和金属-碳键配位到铂中心上,其中氮给体来自吡啶和异喹啉基团,金属-碳键由苯或取代苯和铂形成。该三齿配体带有位于金属-碳键的位置处的形式负电荷(formalnegative charge)。
该三齿配体由结构II表示:
结构II
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。
下面显示该三齿配体的代表性实例:
下面显示基于结构I的铂(II)络合物(络合物1-16)的代表性实例:
在优选实施方案中,提供用代表性实施例中的相应配体(配体1-13)制备铂(II)络合物的通用方法。为制备这些铂(II)络合物,四氯合铂酸钾(potassiumtetrachloroplatinate)(K2PtCl4)和配体(配体1-13)在冰醋酸中的混合物回流24小时,产生黄色悬浮液。该黄色固体用水和丙酮洗涤并在CH2Cl2或DMF中重结晶。下列反应I显示在形成中性铂络合物时优选使用乙酸作为溶剂。
本发明还涉及包含至少一个含有具有结构I的化学结构的有机金属络合物的发光层的OLED。本发明的有机发光器件可包含(优选依次):透明基底;透明电极;空穴传输层;包含被至少一种本发明的有机金属络合物掺杂的基质材料(host material)的发光层;空穴阻挡层;电子传输层;电荷注入层;和电极。本发明的有机发光器件可包含(优选依次):透明基底;透明电极;空穴传输层;包含被至少一种本发明的有机金属络合物掺杂的基质材料的发光层;空穴传输层;包含蓝色至天蓝色光发射材料的发光层;空穴阻挡层;电荷注入层;和电极。如图1中所示,典型器件100具有透明阳极层120;阴极层170;发光层140;任选空穴传输层130;任选空穴阻挡层150和任选电子传输层160。层110是透明基底。本文所用的透明基底可以是玻璃或塑料;刚性或挠性基底。
本发明的有机金属络合物用在发光层140中。层140可以完全由本发明中的有机金属络合物(100重量%有机金属络合物)构成或以一定重量%与基质材料混合。基质材料优选传输空穴和/或电子并具有比本发明中的有机金属络合物宽的带隙。基质材料可以是聚合材料,例如但不限于聚(N-乙烯基咔唑)、聚硅烷和聚芴。其也可以是小分子,例如但不限于CBP(4,4'-N,N'-二咔唑-联苯)或叔芳胺。
本文所用的透明阳极层,如层120可包含或可由含有金属、合金、金属氧化物或混合金属氧化物,如氧化铟锡的材料制成。
本文所用的空穴传输层,如层130可包含或由有机材料,例如但不限于TPD(N,N'-双(3-甲基苯基)-N,N'-二苯基联苯胺)、NPB(N,N'-二-1-萘基-N,N'-二苯基-联苯胺)、TAPC(1,1-双[(二-4-甲苯基氨基)苯基]环己烷)、ETPD(N,N'-双(4-甲基苯基)-N,N'-双(4-乙基苯基)-[1,1'-(3,3'-二甲基)联苯]4,4'-二胺)、CuPc(铜酞菁)、PVK(聚乙烯基咔唑)和PEDOT(聚(3,4-亚乙二氧基噻吩)(poly(3,4-ethylendioxythiophene))制成。
本文所用的空穴阻挡层,如层150可包含或由具有高电子迁移率和低HOMO(最高占据分子轨道)水平的有机材料制成,该有机材料例如但不限于BCP(2,9-二甲基-4,7-二苯基-1,10-菲咯啉,浴铜灵)和BAlq3(双(2-甲基-8-喹啉)(4-苯基苯酚)铝)(BAlq3 (b/s(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum))。
本文所用的电子传输层,如层160可包含或由具有高电子迁移率的有机材料制成,该有机材料例如但不限于Alq3(三(8-喹啉)铝)、BAlq3(双(2-甲基-8-喹啉)(4-苯基苯酚)铝)、PBD(2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-二唑)和TAZ(3-(4-联苯基)-4-苯基-5-(4-叔丁基苯基)-1,2,4-三唑)制成。
本文所用的阴极,如层170可包含或由低功函金属(low work function metal),例如但不限于Ca、Al和Ba制成。本文所用的电极可包含本文所用的阴极和/或本文所用的阳极。
实施例
下面列举许多实施例以进一步阐明本发明。它们不应被视为以任何方式限制本发明。
实施例1
配体1的合成程序:
将1.00克(2.64毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.60克(2.81毫摩尔)3-二甲基氨基-1-(2'-吡啶基)-丙酮盐酸盐和5.00克(64.9毫摩尔)乙酸铵的甲醇(100毫升)溶液回流24小时以产生悬浮溶液。从溶液混合物中过滤粗产物,用水和冷甲醇洗涤,并通过柱色谱法提纯。收率:0.64克(86.0%)。1H NMR (500 MHz, CDCl3) δ = 7.45 (t,J = 7.2 Hz, 1H), 7.55(t, J = 7.2 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.65 (t,J = 7.8 Hz 1H), 7.78 (d, J = 7.5 Hz, 1H), 7.93 (t, J = 7.8 Hz, 1H), 8.02 (d,J = 8.6 Hz, 2H), 8.21 (d, J = 6.3 Hz, 2H), 8.49 (d, J = 7.8 Hz, 1H), 9.01 (s,1H), 9.34 (s, 1H). EI-MS (+ve, m/z): 282 [M+]。
实施例2
配体2的合成程序:
将3-乙酰基异喹啉(0.84克,4.94毫摩尔)和叔丁醇钾(0.83克,7.40毫摩尔)在THF(30毫升)中的溶液在室温下搅拌2小时以产生黄色悬浮液。随后加入1-N,N-二甲基氨基-3-(2',4'-二氟苯基)-3-氧代-1-丙烯(1.04克,4.94毫摩尔)在THF(20毫升)中的溶液并将该混合物在室温下搅拌12小时以产生深红色溶液。将乙酸铵(26.0克,0.34摩尔)在乙酸(100毫升)中的溶液添加到该混合物中。通过蒸馏2小时除去THF,将残留物在真空下干燥。加入二氯甲烷(50毫升)以产生红色溶液,其用饱和碳酸氢钠溶液中和,随后用CH2Cl2萃取。有机萃取物经硫酸钠干燥。通过使用正己烷:乙酸乙酯(9:1)作为洗脱剂的硅胶色谱法进行提纯以产生浅黄色固体。收率:0.94 (60%) 1H NMR (500 MHz, CDCl3) δ = 7.09 (m, 1H),7.11 (m, 1H), 7.62 (t, J = 5.51Hz, 1H), 7.71 (t, J = 8.05 Hz, 1H), 7.78 (d, J= 7.78 Hz, 1H), 7.92 (t, J = 7.83 Hz, 1H), 8.00 (d, J = 8.30 Hz, 1H), 8.01(d, 8.2 Hz, 1H), 8.26 (m, 1H), 8.50 (d, J = 7.6 Hz, 1H), 8.90 (s, 1H), 9.34(s, 1H). EI-MS (+ve, m/z): 319.2[M+]。
实施例3
配体3的合成程序:
将3-乙酰基异喹啉(1.00克,5.84毫摩尔)和叔丁醇钾(0.98克,8.76毫摩尔)在THF(30毫升)中的溶液在室温下搅拌2小时以产生黄色悬浮液。随后加入1-N,N-二甲基氨基-3-(3',4'-二氟苯基)-3-氧代-1-丙烯(1.23克,5.84毫摩尔)在THF(20毫升)中的溶液,并将该混合物在室温下搅拌12小时以产生深红色溶液。将乙酸铵(26.0克,0.34摩尔)在乙酸(acetate acid)(100毫升)中的溶液添加到该混合物中。通过蒸馏2小时除去THF,将残留物真空干燥。加入二氯甲烷(50毫升)以产生红色溶液,其用饱和碳酸氢钠溶液中和,随后用CH2Cl2萃取。有机萃取物经硫酸钠干燥。通过使用正己烷:乙酸乙酯(9:1)作为洗脱剂的硅胶色谱法进行提纯以产生浅黄色固体。收率:0.93克(50%)。1H NMR (500 MHz, CDCl3, 25℃).δ = 7.32 (q, 1H), 7.65 (t, 1H), 7.72 (d, 1H), 7.75 (t, 1H), 7.90 (m, 1H),8.00 (t, 2H), 8.11 (t, 1H), 8.51 (d, 1H), 8.96 (s, 1H), 9.34 (s, 1H). 13C NMR(150 MHz, CDCl3, 25℃): δ = 156.3, 154.4, 152.1, 149.7, 140.0, 136.6, 130.6,128.9, 127.8, 127.7, 127.6, 122.9(3), 122.8, 120.0, 119.6, 117.8, 117.4 (d, J= 17.25 Hz), 116.1 (d, J = 18.15 Hz) EI-MS (+ve, m/z): 319.1 [M+]。
实施例4
配体4-10的通用合成程序
将1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、过量乙酸铵和相应的α,β-不饱和酮的甲醇混合物回流24小时以产生悬浮液混合物。从溶液混合物中过滤粗产物,用水和冷甲醇洗涤,并通过柱色谱法提纯(硅胶,正己烷/Et2O = 8:1作为洗脱剂)。
实施例5
配体4的合成程序:
通过实施例4中的通用程序用1.00克(2.64毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.85克(2.65毫摩尔)3',5'-二-叔丁基苄叉-2-苯乙酮(3',5'-di-tert-butylbenzylidene-2-acetophenone)、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体4。配体4以黄色固体形式获得。收率1.11克(89.0%)。1H NMR (500 MHz, CDCl3, 25℃) δ= 1.47 (s, 18H), 7.51 (m, 1H), 7.58 (m, 3H), 7.65 (t, J = 7.8 Hz, 3H), 7.75(t, J = 7.8 Hz, 1H), 7.90 (s, 1H), 8.01 (m, 2H), 8.23 (d, J = 7.5 Hz, 2H),8.80 (s, 1H), 9.10 (s, 1H), 9.32 (s, 1H). 13C NMR (500 MHz, CDCl3, 25℃): δ =31.6, 35.1, 118.1, 118.3, 118.9, 121.7, 123.1, 127.3, 127.5, 127.6, 127.8,128.3, 128.6, 128.8, 129.0, 130.5, 133.1, 136.7, 138.7, 139.9, 150.3, 151.9.152.0, 156.5.
EI-MS (+ve, m/z): 471 [M+]。
实施例6
配体5的合成程序:
通过实施例4中的通用程序用0.75克(1.97毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.69克(1.97毫摩尔)3',5'-二-叔丁基苄叉-2-(1-乙酰-3-甲氧基苯酮)、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体5。配体5以黄色固体形式获得。收率0.81克(82.0%)。1H NMR (500MHz, CDCl3, 25℃) δ = 1.47 (s, 18H), 3.97 (s, 3H), 7.10 (d,J = 9.4 Hz, 1H), 7.52 (t, J = 7.8 Hz,1H), 7.61 (s, 1H), 7.65 (s, 2H), 7.68(t, J = 7.8 Hz, 1H), 7.79 (t, J = 7.8 Hz, 1H), 7.82 (d, J = 7.5 Hz, 1H), 7.87(s, 1H), 7.97 (s, 1H), 8.04 (d, J = 8.6 Hz, 2H), 8.72 (s, 1H), 9.00 (s, 1H),9.35 (s, 1H). 13C NMR (500 MHz, CDCl3, 25℃): δ = 31.6, 35.1, 55.5, 113.2,114.3, 118.1, 118.5, 119.1, 119.8, 121.7, 123.1, 127.5, 127.6, 127.8, 128.8,129.8, 130.5, 136.7, 138.7, 141.5, 150.3, 151.6, 151.9, 152.0. EI-MS (+ve, m/z): 501 [M+]。
实施例7
配体6的合成程序:
通过实施例4中的通用程序用1.32克(3.51毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、1.28克(3.5毫摩尔)(E)-3-(3,5-二-叔丁基苯基)-1-(3-硝基苯基)丙-2-烯-1-酮、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体6。配体6以黄色固体形式获得。收率:1.12克(62%)。1H NMR (600 MHz, CDCl3, 25℃) δ = 1.44 (s, 18H), 7.59 (d, J =1.5 Hz, 1H), 7.61 (d, J = 1.62 Hz, 2H), 7.66 (t, J = 7.80 Hz), 7.75 (m, 2H),7.98 (d, J = 1.2 Hz, 1H), 8.06 (d, J = 8.10 Hz, 1H), 8.09 (d, J = 8.16 Hz,1H), 8.34 (d, J = 6.12 Hz, 1H), 8.60 (d, J = 7.68 Hz, 1H), 8.81 (s, 1H), 9.04(s, 1H). 9.12 (t, J = 1.62 Hz, 1H), 9.38 (s, 1H). FAB-MS (+ve, m/z): 516.4[M+]。
实施例8
配体7的合成程序:
通过实施例4中的通用程序用0.87克(2.3毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.89克(2.3毫摩尔)3',5'-二-叔丁基苄叉-2-(1-乙酰-3-三氟甲基苯酮)、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体7。配体7以黄色固体形式获得。收率1.05克(85.0%)。1H NMR (500 MHz, CDCl3, 25℃). δ= 1.47 (s, 18H), 7.60 (s, 1H),7.63 (s, 2H), 7.68 (t, J = 7.8 Hz, 1H), 7.72 (t, J = 7.8 Hz, 1H), 7.80 (m,2H), 8.00 (s, 1H), 8.10 (t, J = 8.4 Hz 2H), 8.47 (d, J = 7.5 Hz, 1H), 8.55(s, 1H), 8.80 (s, 1H), 9.00 (s, 1H), 9.35 (s, 1H). 13C NMR (500 MHz, CDCl3, 25℃): δ = 31.6, 35.1, 118.2, 119.0, 121.7, 123.3, 124.1, 124.2, 125.4, 125.5,127.6, 127.7, 127.9, 128.9, 129.2, 130.5, 130.6, 130.9, 131.1, 131.4, 131.6,136.7, 138.5, 140.7, 150.0, 152.1, 151.6. EI-MS (+ve, m/z): 539 [M+]。
实施例9
配体8的合成程序:
通过实施例4中的通用程序用0.62克(1.62毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.52克(1.62毫摩尔)(E)-3-(3,5-二-叔丁基苯基)-(2-氟-4甲氧基苯基)丙-2-烯-1-酮、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体8。配体8以黄色固体形式获得。收率:0.50克(60.0%)。1H NMR (500 MHz, CDCl3). δ = 1.42 (s, 18H), 3.90 (s,3H), 6.76 (d, J = 13 Hz, 1H), 6.93 (d, J = 6.68 Hz), 7.54 (s, 1H), 7.62 (m,3H), 7.72 (t, J = 7.25 Hz, 1H), 8.00 (m, 3H), 8.27 (t, J = 8.9 Hz, 1H), 8.70(d, J = 1.2 Hz, 1H), 8.98 (s, 1H), 9.37 (s, 1H). 13C NMR (500 MHz, CDCl3): δ =31.7, 35.1, 55.7, 101.9, 102.1, 110.7, 117.9, 120.4, 121.8, 122.2, 123.0,127.5, 127.8, 128.8, 130.5, 131.9, 132.0, 136.7, 138.6, 150.3, 151.4, 152.0,153.1, 156.4, 160.6, 161.4, 161.5, 162.6. EI-MS (+ve, m/z): 519.4 [M+]。
实施例10
配体9的合成程序:
通过实施例4中的通用程序用1.00克(2.66毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、0.95克(2.66毫摩尔)3-(2,4-二-叔丁基苯基)-(3,4-二氟苯基)丙-2-烯-1-酮、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体9。配体9以黄色固体形式获得。收率:1.35克(70 %)。
实施例11
配体10的合成程序:
通过实施例4中的通用程序用1.48克(3.93毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、1.40克(3.93毫摩尔)3-(3,5-二-叔丁基苯基)-(3,4-二氟苯基)丙-2-烯-1-酮、5.00克(64.9毫摩尔)乙酸铵和100毫升甲醇合成配体10。配体10以黄色固体形式获得。收率:1.60克(80.0%)。1H NMR (500 MHz, CDCl3). δ = 1.43 (s, 18 H), 7.30-7.36 (m,1H), 7.56 (s, 1H), 7.59 (s, 2H), 7.63 (t, J = 7.2 Hz, H), 7.77 (t, J = 8.0Hz, H), 7.86 (s, 1H, H), 7.94-7.97 (m, 1H), 8.03 (d, J = 7.7 Hz, 1H), 8.06(d, J = 7.8 Hz, 1H), 8.14-8.18 (m, 1H), 8.74 (s, 1H), 9.00 (s, 1H, H), 9.37(s, 1H, H). 13C NMR (126 MHz, CDC13, 25℃):δ = 31.7, 35.1, 116.3, 116.4,117.4, 117.5, 118.1, 118.4, 118.8, 121.7, 12 3.0, 123.2, 127.6, 128.9, 130.6,136.6, 137.0, 138.4, 149.8, 151.7, 151.8, 152.0, 152.2, 154.9, 156.7. 19F NMR(376 MHz, CDCl3, 25℃): δ = -137.4, -137.7. FAB-MS (+ve, m/z): 507 [M+]。
实施例12
配体11的合成程序:
通过实施例4中的通用程序用3.83克(8.97毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、4.20克(8.89毫摩尔)(E)-3-(9,9-二己基-9H-芴-2-基)-1-苯基丙-2-烯-1-酮、7.1克(91毫摩尔)乙酸铵和550毫升甲醇/二氯甲烷(按体积计10:1)混合物合成配体11。配体11以黄色油形式获得。收率:4.35克(82%)。1H NMR (400 MHz, CDCl3): δ 9.39 (s,1H), 9.07 (s, 1H), 8.82 (s, 1H), 8.28 (d, J = 7.3 Hz, 2H), 8.03-8.06 (m, 3H),7.84 (s, 2H), 7.73-7.79 (m, 3H), 7.64 (t, J = 7.0 Hz, 1H), 7.58 (t, J = 7.5Hz, 2H), 7.49 (t, J = 7.5 Hz, 2H), 7.35-7.39 (m, 3H), 2.04-2.12 (m, 4H),1.11-1.23 (m, 12H), 0.73-0.89 (m, 10H). FAB-MS (m/z): 614 [M+]。
实施例13
配体12的合成程序:
通过实施例4中的通用程序用3.83克(8.97毫摩尔)1-(2-氧代-2-(3'-异喹啉基)乙基)碘化吡啶鎓、4.88克(8.97毫摩尔)(E)-3-(7-溴-9,9-二己基-9H-芴-2-基)-1-苯基丙-2-烯-1-酮、15.4克(0.20毫摩尔)乙酸铵和100毫升甲醇/氯仿(按体积计10:1)混合物合成配体12。配体12以黄色油形式获得。收率:4.52克(73%)。1H NMR (400 MHz, CDCl3): δ 9.39(s, 1H), 9.08 (s, 1H), 8.81 (s, 1H), 8.28 (d, J = 8.5 Hz, 2H), 8.05 (d, J =8.9 Hz, 2H), 8.01 (s, 1H), 7.74-7.86 (m, 4H), 7.61-7.67 (m, 2H), 7.59 (t, J =7.6 Hz, 2H), 7.49-7.51 (m, 3H), 2.01-2.10 (m, 4H), 1.06-1.18 (m, 12H), 0.65-0.86 (m, 10H). FAB-MS (m/z): 694 [M+]。
实施例14
配体13的合成程序:
通过注射器将2 M Na2CO3水溶液(15毫升)注射到1.03克(1.48毫摩尔)配体12、0.17克(0.154毫摩尔)四(三苯膦)钯(0)和0.68克(1.48毫摩尔)9,9-二-正己基芴-2-基-4,4,5,5-四甲基-[1,3,2]二氧杂环戊硼烷(dioxaborolane)的脱气甲苯溶液(150毫升)中。将反应混合物在80℃下搅拌12小时。产物用二氯甲烷萃取(3 x 100毫升),用水洗涤并经MgSO4干燥。在溶剂蒸发后,残留物通过利用硅胶使用CH2Cl2作为洗脱剂的快速色谱法提纯,以获得浅黄色油形式的配体13。收率:0.89克,64%。1H NMR (400 MHz, CDCl3): δ 9.40 (s, 1H), 9.09(s, 1H), 8.85 (s, 1H), 8.30 (d, J = 7.6 Hz, 2H), 8.04-8.06 (m, 3H), 7.63-7.88(m, 12H), 7.59 (t, J = 7.6 Hz, 2H), 7.50 (t, J = 7.6 Hz, 1H), 7.30-7.38 (m,3H), 2.12-2.17 (m, 4H), 2.02-2.07 (m, 4H), 1.02-1.18 (m, 24H),0.72-0.83 (m,20H). FAB-MS (m/z): 947 [M+]。
实施例15
络合物1-14的通用合成程序
将K2PtCl4和配体1-14在冰醋酸(100毫升)中的混合物回流48小时以产生黄色悬浮液形式的络合物1至14。过滤黄色固体,用水和丙酮洗涤并在DMF中重结晶。
实施例16
络合物1的合成程序:
通过实施例15中的通用程序用0.42克(1.01毫摩尔)K2PtCl4、0.23克(0.82毫摩尔)配体1和100毫升冰醋酸合成络合物1。络合物1以黄色结晶固体形式获得。收率:0.34克(80.0%)。1H NMR (400 MHz, DMF, 25℃):δ = 7.12 (t, J = 6.9 Hz, 1H), 7.20 (t, J= 6.9 Hz, 1H), 7.68 (d, J = 6.6 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.97 (m,1H), 8.11 (t, J = 7.3 Hz 1H), 8.22 (m, 4H), 8.54 (d, J = 7.5 Hz, 1H), 9.15(S1 1H), 9.75 (s, 1H). 13C NMR (500 MHz, CDCl3, 25℃): δ = 119.4, 123.1,124.4, 125.2, 128.8, 130.0, 130.3, 130.7, 130.9, 131.4, 134.5, 135.3, 136.7,140.1, 143.7, 148.0, 151.0, 152.7, 155.6, 163.2. FAB-MS (+ve, m/z): 512 [M+]。
实施例17
络合物2的合成程序:
通过实施例15中的通用程序用0.49克(1.17毫摩尔)K2PtCl4、0.31克(0.98毫摩尔)配体2和100毫升冰醋酸合成络合物2。络合物2以黄色结晶固体形式获得。收率:0.43克(80.0%)。1H NMR (500 MHz, DMF) δ = 7.37 (t, J = 8.44 Hz, 1H), 7.44 (t, J =9.98 Hz, 1H), 8.03 (d, J = 7.75 Hz, 1H), 8.11 (m, 1H), 8.32 (t, J = 7.6 Hz),8.44 (d, J = 8.15 Hz, 1H), 8.67 (t, J = 7.85 Hz, 1H), 8.73 (d, J = 7.95 Hz,1H), 8.92 (d, J = 8.13 Hz), 9.44 (s, 1H), 10.39 (s, 1H). 13C NMR (500 MHz,CDCl3): δ = 103.9, 104.0, 111.5, 121.8, 123.4, 128.4, 129.6, 130.2, 131.5,134.0, 134.6, 135.9, 140.3, 151.2, 153.2, 157.4, 159.9, 162.7, 163.0, 164.1。
实施例18
络合物3的合成程序:
通过实施例15中的通用程序用0.78克(1.88毫摩尔)K2PtCl4、0.50克(1.57毫摩尔)配体3和100毫升冰醋酸合成络合物3。络合物3以黄绿色结晶固体形式获得。收率:0.69克(80.0%)。FAB-MS (+ve, m/z): 512 [M-Cl+]。
实施例19
络合物4的合成程序:
通过实施例15中的通用程序用0.31克(0.75毫摩尔)K2PtCl4、0.29克(0.62毫摩尔)配体4和100毫升冰醋酸合成络合物4。络合物4以黄色结晶固体形式获得。收率:0.39克(90.0%)。1H NMR (400 MHz, DMF, 25℃): δ =1.47 (s, 18H), 7.10 (m, 2H), 7.67 (d,J = 6.6 Hz, 1H), 7.77 (s, 1H), 7.79 (d, J = 6.7 Hz, 1H), 7.92 (t, J = 7.3 Hz,1H), 7.97 (s, 2H), 8.08 (t, J = 7.6 Hz, 1H), 8.12 (d, J = 4.2 Hz, 2H), 8.39(d, J = 8.1Hz, 1H), 8.54 (s, 1H), 9.27 (s, 1H), 9.65 (s, 1H). 13C NMR (500MHz, CDCl3, 25℃): δ = 31.5, 35.7, 117.4, 117.8, 122.7, 123.3, 123.4, 124.2,124.7, 125.5, 128.7, 129.9, 130.2, 130.4, 131.2, 134.3, 135.2, 136.7, 137.9,143.7, 148.2, 151.2, 152.5, 152.9, 155.5, 162.3. FAB-MS (+ve, m/z): 700 [M+]。
实施例20
络合物5的合成程序:
通过实施例15中的通用程序用0.37克(0.90毫摩尔)K2PtCl4、0.28克(0.54毫摩尔)配体5和100毫升冰醋酸合成络合物5。络合物5以黄色结晶固体形式获得。收率:0.28克(70.0%)。1H NMR (500 MHz, DMF, 25℃): δ = 1.47 (s, 18H), 3.93 (s, 3H), 6.90(d, J = 7.7 Hz, 1H), 7.54 (s, 1H), 7.60 (d, J = 8.3 Hz, 1H), 7.73 (s, 1H),7.95 (m, 3H), 8.12 (t, J = 7.5 Hz, 1H), 8.17 (d, J = 8.1Hz, 1H), 8.33 (s,1H), 8.52 (d, J = 8.1Hz, 1H), 8.58 (s, 1H), 9.32 (s, 1H), 9.75 (s, 1H). 13CNMR (500 MHz, DMF, 25℃): δ = 31.6, 35.7, 111.6, 116.7, 117.7, 118.0, 122.8,123.4, 124.7, 128.7, 129.9, 130.3, 131.3, 133.5, 134.3, 135.8, 136.6, 138.0,148.7, 151.2, 152.3, 152.4, 153.1, 155.6, 158.1, 162.5 FAB-MS (+ve, m/z): 730[M+]。
实施例21
络合物6的合成程序:
通过实施例15中的通用程序用0.17克(0.45毫摩尔)K2PtCl4、0.18克(0.35毫摩尔)配体6和100毫升冰醋酸合成络合物6。络合物6以黄色结晶固体形式分离。收率:0.23克(90.0%)。1H NMR (500 MHz, CD2Cl2, 25℃): δ = 1.50 (s, 18H), 7.12 (s, 1H), 2.93(m, 2H), 7.44 (d, J = 7.55 Hz, 1H), 7.55 (t, J = 6.85 Hz, 1H), 7.66 (s, 2H),7.70 (m, 3H), 7.76 (t, J = 7.15 Hz, 1H), 7.81 (d, J = 8.05 Hz, 1H), 8.13 (s,1H), 8.91 (s, 1H). FAB-MS (+ve, m/z): 745.2[M+]。
实施例22
络合物7的合成程序:
通过实施例15中的通用程序用0.19克(0.46毫摩尔)K2PtCl4、0.20克(0.38毫摩尔)配体7和100毫升冰醋酸合成络合物7。络合物5以黄色结晶固体形式获得。收率:0.20克(70.0%)。1H NMR (500 MHz, DMF, 25℃): δ = 1.47 (s, 18H), 7.37 (d, J = 7.7 Hz,1H), 7.75 (s, 1H), 7.80 (d, J = 7.8 Hz, 1H), 7.90 (t, J = 7.1Hz, 1H), 7.98(s, 2H), 8.10 (m, 2H), 8.30 (d, J = 8.0 Hz, 1H), 8.40 (s, 2H), 8.60 (s, 1H),9.25 (s, 1H), 9.50 (s, 1H). 13C NMR (500 MHz. DMF, 25℃): 8 = 31.5, 35.7,117.6, 118.4, 118.7, 121.4, 121.7, 121.9, 122.1, 122.9, 123.3, 123.7, 124.9,125.6, 126.4, 127.1, 128.8, 130.0, 131.4, 134.1, 134.5, 135.3, 136.7, 137.7,142.3, 146.2, 146.9, 162.7. FAB-MS (+ve, m/z): 768 [M+]。
实施例23
络合物8的合成程序:
通过实施例15中的通用程序用0.17克(0.45毫摩尔)K2PtCl4、0.44克(0.86毫摩尔)配体8和100毫升冰醋酸合成络合物8。络合物8以橙色结晶固体形式获得。收率:0.52克(80.0%)。1H NMR (500 MHz, DMF, 25℃): δ= 1.64 (s, 18H), 3.73 (s, 3H), 6.59 (d,J = 14.1Hz, 1H), 7.00 (d, J = 2.4 Hz, 1H), 7.80 (s, 1H), 7.90 (t, J = 1.6 Hz1H), 8.00 (t, J = 7.8 Hz, 1H), 8.04 (d, J = 1.7 Hz, 2H), 8.21 (m, 1H), 8.27(d, J = 4.05 Hz, 1H), 8.29 (d, J = 4.3 Hz, 1H), 8.49 (s, 1H), 9.28 (s, 1H),9.59 (s, 1H). 13C NMR (126 MHz, DMF, 25℃):δ = 30.0, 35.2, 97.4, 115.6, 116.7,119.2, 119.3, 122.2, 123.0, 124.2, 126.7, 128.3, 129.2, 129.5, 130.7, 133.8,136.2, 137.9, 145.9, 151.0, 152.0, 152.1, 155, 160.1, 162.1, 162.4, 162.6,163.2, 163.8. FAB-MS (+ve, m/z): 748.2[M+]。
实施例24
络合物9的合成程序:
通过实施例15中的通用程序用0.49克(1.18毫摩尔)K2PtCl4、0.50克(0.99毫摩尔)配体9和100毫升冰醋酸合成络合物9。络合物8以橙色结晶固体形式获得。收率:0.58克(80.0%)。1H NMR (500 MHz, CD2Cl2, 25℃): δ = 1.48 (s, 18H), 6.39-6.44 (m, 1H),6.97 (d, J = 8.5 Hz, 1H), 7.63-7.67 (m, 5H), 7.73 (d, J = 8.2 Hz), 7.80-7.83(m, 2H), 7.91 (d, J = 8.2 Hz, H), 8.33 (s, 1H), 9.24 (s, 1H). 13C NMR (126MHz, CD2Cl2, 25℃):δ = 31.4, 35.2, 99.0, 99.2, 116.7, 116.8, 120.1, 120.3,121.8, 121.9, 124.3, 127.9, 128.7, 129.2, 130.2, 133.2, 135.7, 137.4, 150.6,152.1, 152.2, 152.6, 154.4. 19F NMR (400 MHz, CD2Cl2, 25℃): δ= -105.9, -111.3。
实施例25
络合物10的合成程序:
通过实施例15中的通用程序用0.93克(2.37毫摩尔)K2PtCl4、1.00克(1.97毫摩尔)配体10和100毫升冰醋酸合成络合物10。络合物10以黄色固体形式获得。收率:0.87克(60.0%)。1H NMR (500 MHz, CD2Cl2, 25℃):δ = 1.49 (s, 18H), 6.97-7.01 (m, 1H),7.06-7.10 (m, 2H), 7.60-7.68 (m, 5H), 7.74 (S, 1H), 7.83 (t, J = 8.1Hz, H),7.92 (d, J = 8.1Hz, H), 8.25 (s, 1H), 9.17 (s, 1H). 13C NMR (126 Hz, CD2Cl2,25℃): δ= 31.4, 35.2, 112.3, 112.4, 116.5, 117.1, 121.7, 121.9, 122.0, 124.4,127.8, 127.9, 128.6, 129.1, 130.2, 133.2, 135.5, 137.2, 139.1, 150.4, 152.0,152.3, 152.4, 154.6, 163.0. 19F NMR (400 MHz, CDCl3, 25℃): δ = -134.3, -146.0. FAB-MS (+ve, m/z): 700 [M-Cl]+。
实施例26
络合物11的合成程序:
通过实施例15中的通用程序用0.93克(2.37毫摩尔)K2PtCl4、1.00克(1.97毫摩尔)配体10和100毫升冰醋酸合成络合物11。络合物11以黄色固体形式获得。收率:0.44克(30.0%)。1H NMR (500 MHz, CD2Cl2, 25℃): δ= 1.54 (s, 18H), 6.80 (m, 1H), 7.18(m, 1H), 7.39 (s, 1H), 7.65 (s, 2H), 7.68 (s, 1H), 7.69 (t, J = 7.2 Hz, 1H),7.82 (s, 1H), 7.87 (m, 2H), 7.98 (d, J = 8.1Hz, 1H), 8.36 (s, 1H), 9.59 (s,1H). 13C NMR (126 MHz, CD2Cl2, 25℃): δ = 31.4, 35.2, 112.1, 112.3, 116.9,117.3, 120.8, 121.6, 121.7, 124.5, 127.9, 129.0, 129.1, 130.4, 133.6, 135.7,137.2, 150.7, 151.3, 152.3, 152.7, 154.7, 163.9. 19F NMR (376 MHz, CDCl3, 25℃): -121.9, -132.5. FAB-MS (+ve, m/z): 700 [M-Cl]+。
实施例27
络合物12的合成程序:
通过实施例15中的通用程序用0.71克(1.71毫摩尔)K2PtCl4、1.05克(1.71毫摩尔)配体11和50毫升冰醋酸合成络合物12。络合物12以黄色固体形式获得。收率:1.3克(86%)。1HNMR (400 MHz, CD2Cl2): δ 9.70 (s, 1H), 8.51 (s, 1H), 8.11 (d, J = 8.0 Hz, 1H),8.04 (d, J = 8.2 Hz, 1H), 7.98 (s, 1H), 7.92-7.96 (m, 2H), 7.785-7.85 (m,3H), 7.69 (t, J = 6.4 Hz, 1H), 7.50 (d, J = 7.5 Hz, 1H), 7.39-7.45 (m, 3H),7.18 (t, J = 6.4 Hz, 1H), 7.13 (t, J = 7.5 Hz, 1H), 2.08-2.16 (m, 4H), 1.08-1.39 (m, 12H), 0.69-0.89 (m, 10H). FAB-MS (m/z): 844 [M+]。
实施例28
络合物13的合成程序:
通过实施例15中的通用程序用0.71克(1.71毫摩尔)K2PtCl4、1.19克(1.71毫摩尔)配体12和50毫升冰醋酸合成络合物13。络合物13以黄色固体形式获得。收率:1.3克(86%)。1HNMR (400 MHz, CD2Cl2): δ 9.33 (S, 1H), 8.39 (s, 1H), 7.86-7.93 (m, 5H), 7.82(t, J = 7.5 Hz, 1H), 7.72-7.76 (m, 2H), 7.55-7.63 (m, 3H), 7.47 (d, J = 7.4Hz, 1H), 7.30 (s, 1H), 7.23 (d, J = 7.0 Hz, 1H), 6.99 (t, J = 7.2 Hz, 1H),6.94 (t, J = 7.2 Hz, 1H), 2.19-2.25 (m, 2H), 2.02-2.13 (m, 2H), 2.02-2.09 (m,4H), 1.11-1.22 (m, 12H), 0.72-0.81 (m, 10H). FAB-MS (m/z): 923 [M+]。
实施例29
络合物14的合成程序:
通过实施例15中的通用程序用0.71克(1.71毫摩尔)K2PtCl4、1.62克(1.71毫摩尔)配体13和50毫升冰醋酸合成络合物14。络合物9以橙色固体形式获得。收率:1.3克,86%。1HNMR (400 MHz, CD2Cl2): δ 9.56 (s, 1H), 8.48 (s, 1H), 7.83-8.02 (m, 8H), 7.64-7.77 (m, 6H), 7.60-7.63 (m, 2H), 7.57 (S, 1H), 7.49 (t, J = 7.3 Hz, 1H), 7.42(m, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.08 (m, 2H), 2.23-2.33 (m, 2H), 2.06-2.15(m, 2H), 1.01-1.38 (m, 12H), 0.76-0.87 (m, 10H). FAB-MS (m/z): 1177 [M+]。
实施例30
络合物15的合成程序:
将络合物4(0.17克,0.24毫摩尔)、1-乙基-4-甲基苯(0.18毫升,1.43毫摩尔)和三乙胺(1毫升,6.68毫摩尔)溶解在乙腈:二氯甲烷(3:1)溶液(30毫升)中。将CuI(5毫克)作为催化剂添加剂到反应混合物中。该黄色混合物在氮气下在室温下搅拌48小时。随后过滤橙色固体并用冷乙腈和二乙醚洗涤。随后将固体干燥以产生橙色络合物15。收率:0.16克(84%)。FAB-MS (+ve, m/z): 779 [M+]。
实施例30a
络合物16的合成:
将络合物14(100毫克,0.085毫摩尔)、2,6-二甲基苯基异腈化物(12毫克,0.086毫摩尔)和过量NH4PF6(500毫克,3.06毫摩尔)在CH2Cl2/CH3CN溶液(v.v,1:1)中的混合物搅拌12小时以产生黄色溶液形式的络合物16。在减压下除去溶剂以产生橙色固体。收集所得橙色固体,用大量的H2O、CH3CN和Et2O洗涤,随后干燥。通过正己烷分层到浓CH2Cl2溶液上,以橙色晶体形式分离纯产物(108毫克,收率90%)。FAB-MS (+ve m/z): 1270 [M-PF6]+. 1H NMR(CD2Cl2): δ 0.70-0.72 (m, 4H, -CH2-), 0.76-0.79 (m, 16H, -CH2-和-CH3), 1.08-1.26 (m, 24H, -CH2-), 2.06-2.11 (m, 4H, -CH2-), 2.22-2.42 (m, 4H, -CH2-), 2.62(s,6H), 7.21 (t, J = 8.9 Hz, 1H), 1.21-1 Al (m, 7H), 7.44-7.51 (m, 1H), 7.68-7.71 (m, 3H), 7.45-7.77 (m, 3H), 7.82-7.85 (m, 2H), 7.89-7.93 (m, 3H), 7.95-8.03 (m, 3H), 8.15 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 8.2 Hz, 1H), 8.30 (s,1H), 9.80 (s, 1H), 9.48 (s, 1H)。
实施例31
实施例31阐明制备本发明中的OLED的通用程序。在具有20 Ω/☐薄层电阻(sheetresistance)的图案化氧化铟锡(ITO)玻璃上制备OLED。继续在薄膜沉积系统(与EdwardsAuto 306沉积系统集成的MBraun三手套箱系统(three-glove box system))中在1×10-6torr的真空下进行材料的热真空沉积。使用阳极化铝铝盖密封该器件并使用Photoresearch PR-650检查它们的性能。使用Keithley 2400源表(sourcemeter)研究电流-电压特性。使用络合物1-6和14的OLED具有下列构造:ITO(氧化铟锡)/ NPB(4,4'-双[N-(1-萘基)-N-苯基氨基]联苯,40 nm)/CBP(4,4'-N,N'-二咔唑联苯:络合物1-6和14,X%,30nm)/BCP(浴铜灵,15 nm)/Alq3(三(8-喹啉)铝,30 nm)/LiF(0.5 nm)/ Al(100 nm)。
实施例32
实施例32阐明通过实施例31中所述的方法使用络合物1-6和14作为发光材料制成的OLED器件的器件性能。
实施例33
实施例33阐明制备本发明中的OLED的通用程序。在具有20 Ω/☐薄层电阻的图案化氧化铟锡(ITO)玻璃上制备OLED。继续在薄膜沉积系统(与Edwards Auto 306沉积系统集成的MBraun三手套箱系统)中在1×10-6 torr的真空下进行材料的热真空沉积。使用阳极化铝铝盖密封该器件,并使用Photoresearch PR-650检查它们的性能。使用Keithley 2400源表研究电流-电压特性。使用络合物13的OLED具有下列构造:ITO(氧化铟锡)/ NPB(4,4'-双[N-(1-萘基)-N-苯基氨基]联苯,40 nm)/CBP(4,4'-N,N'-二咔唑联苯:络合物13,3.5%,20nm)/BCP(浴铜灵,40 nm)/LiF(0.5 nm)/ Al(100 nm)(器件H)。图21显示器件H的J-V-B曲线。在1 cd/m2下的阈电压为<54 V。器件H在14V下表现出8270 cd m-2的最大亮度(luminance)。
实施例34
实施例34阐明制备本发明中的WOLED(器件I)的通用程序。在具有20 Ω/☐薄层电阻的图案化氧化铟锡(ITO)玻璃上制备WOLED。继续在薄膜沉积系统(与Edwards Auto 306沉积系统集成的MBraun三手套箱系统)中在1×10-6 torr的真空下进行材料的热真空沉积。使用阳极化铝铝盖密封该器件,并使用Photoresearch PR-650检查它们的性能。使用Keithley2400源表研究电流-电压特性。使用络合物的WOLED具有下列构造:ITO(氧化铟锡)/ NPB(4,4'-双[N-(1-萘基)-N-苯基氨基]联苯,40 nm)/CBP(4,4'-N,N'-二咔唑联苯:络合物12,4.2%,20 nm)/NPB(2 nm)/9,10-双-(2-萘基)-蒽烯(DNA, 1nm)/BCP(浴铜灵,40 nm)/LiF(0.5 nm)/ Al(100 nm)(器件I)。图24显示器件I的J-V-B曲线。在1 cd/m2下的阈电压为<5V。器件H表现出在13V下7996 cd m-2的最大亮度和(0.32, 0.31)的CIE。
Claims (15)
1.具有结构I的化学结构的有机金属络合物:
结构I
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基;X是卤素,
其中A是碳、氮、氧、硅、磷、硫、砷和硒;B是连接R17和R19的化学键、
R6-R15独立地为氢、烷基、取代烷基、环烷基、芳基和取代芳基;R16-R23独立地为碳、氮、氧、硅、磷、硫、砷和硒;Z1- Z4以及Z6-Z9独立地为氢、烷基、取代烷基、环烷基、芳基、取代芳基,Z5为烷基、取代烷基、环烷基、芳基、取代芳基,且Z1-Z8可以与相邻基团形成5-7元环。
2.权利要求1的有机金属络合物,其中结构I是下列化合物之一:
。
3.包括含有一种或多种如权利要求1中所述的有机金属络合物的发光材料的有机发光器件。
4.如权利要求3中所述的有机发光器件,其中该络合物具有下列结构之一:
。
5.如权利要求3或4中所述的有机发光器件,其中通过热沉积在该器件中以层形式施加该有机金属络合物。
6.如权利要求3至5任一项中所述的有机发光器件,其中通过旋涂在该器件中以层形式施加该有机金属络合物。
7.如权利要求3至6任一项中所述的有机发光器件,其中通过喷墨印刷在该器件中以层形式施加该有机金属络合物。
8.如权利要求3至7任一项中所述的有机发光器件,其中在对层施加电流时该器件发射单色。
9.如权利要求3至8任一项中所述的有机发光器件,其中在对含有所述一种或多种如权利要求1或2中所述的有机金属络合物的层施加电流时和在对一个或多个由其它发光材料制成的发光部件施加电流时,该器件发射白光。
10.有机发光器件,其包含
透明基底;
透明电极;
空穴传输层;
发光层,其包含被至少一种如权利要求1或2中所述的有机金属络合物掺杂的基质材料;
空穴阻挡层;
电子传输层;
电荷注入层;和
电极。
11.有机发光器件,其包含:
透明基底;
透明电极;
空穴传输层;
发光层,其包含被至少一种如权利要求1或2中所述的有机金属络合物掺杂的基质材料;
空穴传输层;
包含蓝色至天蓝色光发射材料的发光层;
空穴阻挡层;
电荷注入层;和
电极。
12.制造根据权利要求1的有机金属络合物的方法,包括:
使用乙酸作为溶剂使如下列结构II确定的相应配体与四氯合铂酸钾(K2PtCl4)反应以形成具有结构I的化学结构的有机金属络合物:
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。
13.具有下列结构的化合物:
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基。
14.具有下列结构之一的化合物:
。
15.制造有机发光器件的方法,包括下列步骤:
使具有下列结构的配体与四氯合铂酸钾(K2PtCl4)反应以获得铂络合物:
其中R1-R5独立地为氢、卤素、羟基、未取代烷基、取代烷基、环烷基、未取代芳基、取代芳基、酰基、烷氧基、酰氧基、氨基、硝基、酰基氨基、芳烷基、氰基、羧基、硫代、苯乙烯基、氨基羰基、氨基甲酰基、芳氧基羰基、苯氧基羰基或烷氧基羰基;和
作为发光器件的发光层施加该络合物层或在发光器件的发光层中掺入该络合物。
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WO2010145190A1 (en) | 2010-12-23 |
EP2443132A4 (en) | 2013-01-02 |
CN102482309A (zh) | 2012-05-30 |
JP5684247B2 (ja) | 2015-03-11 |
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