CN111320626A - 有机电致发光材料、其制备方法及有机电致发光器件 - Google Patents
有机电致发光材料、其制备方法及有机电致发光器件 Download PDFInfo
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- CN111320626A CN111320626A CN201811544417.9A CN201811544417A CN111320626A CN 111320626 A CN111320626 A CN 111320626A CN 201811544417 A CN201811544417 A CN 201811544417A CN 111320626 A CN111320626 A CN 111320626A
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- organic electroluminescent
- compound
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- organic
- electroluminescent material
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- 239000010410 layer Substances 0.000 claims description 64
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- 239000012044 organic layer Substances 0.000 claims description 15
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- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
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- 150000002431 hydrogen Chemical class 0.000 claims description 6
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- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical group C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 3
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- WUNJCKOTXFSWBK-UHFFFAOYSA-N indeno[2,1-a]carbazole Chemical class C1=CC=C2C=C3C4=NC5=CC=CC=C5C4=CC=C3C2=C1 WUNJCKOTXFSWBK-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 claims description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 3
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- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
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- 239000002253 acid Substances 0.000 description 1
- 150000001251 acridines Chemical group 0.000 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
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- 230000008878 coupling Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- GRRGWAJRNUTOFH-UHFFFAOYSA-N imidazo[1,5-a][1,8]naphthyridine Chemical compound C1=CC2=C(N=C1)N3C=NC=C3C=C2 GRRGWAJRNUTOFH-UHFFFAOYSA-N 0.000 description 1
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- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GFOZRCASAHKFFT-UHFFFAOYSA-N spiro[10h-acridine-9,9'-fluorene] Chemical compound C12=CC=CC=C2NC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 GFOZRCASAHKFFT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- 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]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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Abstract
本发明提供了有机电致发光材料、其制备方法及有机电致发光器件。本发明有机电致发光材料为基于咪唑[1,5‑a][1,8]萘啶的一类化合物，具有如下式I所述的结构。本发明还提供该材料在有机发光二极管(OLED)中的应用。本发明的化合物具有高的稳定性，本发明制备的有机电致发光器件具有高的效率。
Description
技术领域
本发明涉及有机电致发光材料领域，具体涉及一种基于咪唑[1,5-a][1,8]萘啶化合物，还涉及一种发光器件。
背景技术
OLED即有机发光二极管(Organic Light-Emitting Diode)或有机发光器件(Organic Light-Emitting)。OLED是自主发光器件，无需背光源，具有响应速度快、驱动电压低、发光效率高、分辨率高、视角广等特点，已经成为新一代显示和照明技术，特别是在手机、电脑、电视、可弯曲和折叠的电子产品有着巨大的应用前景。
目前有两类发光材料应用于OLED：荧光材料和磷光材料。早期器件所采用的发光材料主要为有机小分子荧光材料，而自旋统计量子学表明荧光材料的理论内部量子效率仅为25％。1998年美国普林斯顿大学的Forrest教授和南加州大学的Thompson教授发现了室温下金属有机配合物分子材料的磷光电致发光现象，利用重金属原子的强自旋轨道耦合可以有效促进电子由单线态到三线态的系间窜越(ISC)，从而OLED器件可以充分利用电激发所产生的单线态和三线态激发子，使发光材料的理论内部量子效率可达到100％(Nature,1998,395,151)。
在OLED材料中，由于大部分的有机电致发光材料传输空穴的速度要比传输电子的速度要大一两个数量级，容易造成发光层的电子和空穴数量不平衡，因此得到的器件效率也比较低。因此对发光层中的主体材料选择和优化，对于提高有机电致发光器件的效率以及寿命有很大的影响。CBP自发明以来，已经被广泛应用于磷光器件的发光层中。虽然其中的咔唑基团导致CBP具有较高的三线态能级，可用于磷光材料的发光层中，但其主要为空穴传输型的材料，对于电子传输的速度较低，因此极易造成载流子注入及传输不平衡。另外，CBP的玻璃化转变温度Tg较低，不利于器件的稳定使用。因此，发展稳定性高的，载流子传输平衡的发光层主体材料，对于有机电致发光器件的广泛使用具有重大的价值。
发明内容
本发明提供了一种基于咪唑[1,5-a][1,8]萘啶化合物，具有较好的热稳定性，高的空穴/电子传输平衡能力。本发明还提供该材料在有机发光二极管(OLED)中的应用，采用该有机电致发光化合物制备的器件具有电致发光效率好，色纯度优以及寿命长的有点。
有机电致发光材料，为具有如下结构式I的化合物：
其中Ar选自C6-C30取代或未取代的芳基、C5-C30的取代或未取代的含有一个或多个杂原子的芳基、N-芳基取代的咔唑基、N-芳基取代的茚并咔唑衍生物取代基、二芳胺基、R1-R8取代的二芳胺基及其环状衍生物Cy，Z为C(R9)2、Si(R9)2、O、S、NR9、SO2，其中R1-R9为独立地为氢、氘、卤素、未取代的烷基、卤代的烷基、氘代的烷基、环烷基、未取代的芳基、烷基取代的芳基、烷氧基、氰基、咔唑基、二苯胺基、或者R1-R9独立地与邻近的基团形成5-8元环，
Cy：
L选自亚苯基、亚联苯基、亚萘基；
R选自氢、氘、取代或未取代的C6-C10的芳基、C6-C10的杂芳基。
Ar选自苯基、萘基、联苯基、菲基、蒽基、芳基蒽基、芘基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、吡啶基、嘧啶基、喹啉基、异喹啉基、三嗪基、吡咯基、呋喃基、噻唑基、喹唑啉基、三氮唑基、苯并噻唑基、苯并噻二唑基、1,2,4-三唑基、三苯胺基、芳基咔唑基、N-芳基取代的咔唑基、二苯胺基、吖啶基及吖啶衍生物取代基、吩噁嗪基及其衍生物取代基、吩噻嗪基及其衍生物取代基；R选自氢、苯基、萘基、吡啶基。
Ar优选自苯基、萘基、联苯基、菲基、蒽基、芳基蒽基、芘基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、嘧啶基、三嗪基、喹唑啉基、1,2,4-三唑基、N-苯基-咔唑基、二苯胺基、吖啶基及吖啶衍生物取代基。
具有结构I的化合物的某些具体非限制实例如下：
上述有机电致发光材料的制备方法，包括如下步骤：
(1)提供化合物A，
(2)在碱性条件下，以四三苯基膦钯为催化剂，将含有Ar的硼酸化物或含有Ar的频哪醇硼酸酯与化合物A发生反应，得到式(I)化合物，
A:
所述化合物A的制备方法如下：
A)在正丁基锂作用下，2-溴-1,8-二萘啶与R的甲酸酯发生反应得到化合物B，
B)化合物B与溴代L的甲醛化合物CHO-L-Br发生反应制得化合物A。
所述R的甲酸酯为R的甲酸甲酯。
本发明的咪唑[1,5-a][1,8]萘啶化合物可以应用于有机电致发光器件、太阳能电池、有机薄膜晶体管或者有机感受器领域。
本发明还提供了一种有机电致发光器件，该器件包含阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、电子注入层及电子传输层中的至少一层，所述有机层中至少一层含有如结构式I所述的咪唑[1,5-a][1,8]萘啶化合物。
其中Ar、L、R的定义如前所述。
其中有机层为发光层和电子传输层；
或者有机层为发光层、空穴注入层、空穴传输层和电子传输层；
或者有机层为发光层、空穴注入层、空穴传输层、电子传输层和电子注入层；
或者有机层为发光层、空穴传输层、电子传输层、电子注入层；
或者有机层为发光层、空穴传输层、电子注入层；
优选地，其中如结构式I所述的基于咪唑[1,5-a][1,8]萘啶化合物所在的层为发光层。
优选地，其中结构式I所述的含有咪唑[1,5-a][1,8]萘啶化合物为结构式1-36的化合物；
如结构式I所述的含有咪唑[1,5-a][1,8]萘啶化合物用于发光器件制备时，可以单独使用，也可以和其它化合物混合使用，也可以同时使用结构式I中的两种以上的化合物。
本发明的有机电致发光器件，进一步优选的方式为，该有机电致发光器件包含阳极、空穴传输层、发光层、电子传输层、电子注入层和阴极，其中发光层中含有结构式I的化合物，进一步优选，发光层中含有化合物为结构的1-36的化合物。
本发明的有机电致发光器件有机层的总厚度为1-1000nm，优选50-500nm。
本发明的有机电致发光器件在使用本发明具有结构式I的化合物时，可以搭配使用其它材料，而获得蓝光、绿光、黄光、红光或者白光。
本发明的有机电致发光器件中的有机层的每一层，可以通过真空蒸镀法、分子束蒸镀法、溶于溶剂的浸涂法、棒涂法或者喷墨打印等方法制备。对于金属电机可以使用蒸镀法或者溅射法进行制备。
器件实验表明，本发明如结构式I所述的含有咪唑[1,5-a][1,8]萘啶化合物具有较好的热稳定性，高的空穴/电子传输平衡能力。采用该有机电致发光化合物制备的器件具有电致发光效率好，色纯度优以及寿命长的有点。
附图说明
图1化合物29的DSC图谱，
图2有机电致发光器件结构示意图，110代表为玻璃基板，120代表为阳极，130代表为空穴注入层，140代表为空穴传输层，150代表为发光层，160代表为电子传输层，170代表为电子注入层，180代表为阴极。
具体实施方式
以下为说明实施本发明的实施方案的实施例。这些实施例不应解释为限制性。除非另外提到，所有百分数均以重量计，所有溶剂混合物比例均为体积比。
中间体的合成
中间体1的合成
在三口烧瓶中加入2-溴-1,8-二萘啶(10g,47.84mmol)，无水THF(100ml)，氮气保护，在-50℃中搅拌20分钟后，通过恒压滴液漏斗滴加正丁基锂的正己烷溶液(2.2M,26ml,57mmol)，滴加完毕后继续保持温度搅拌半小时，随后滴加苯甲酸甲酯的THF溶液(6.84g,50.2mmol)，随后缓慢升温至室温，搅拌过夜。反应结束后，用饱和氯化铵溶液淬灭反应，分离有机相，无机相用乙酸乙酯萃取，合并有机相，产物经柱层析纯化得到7.7g，产率71％。
中间体2的合成
合成原料为4-吡啶甲酸甲酯，合成方法与中间体1的一致，产率为68％。
中间体3的合成
在烧瓶中，加入中间体1(3g,12.8mmol)，对溴苯甲醛(2.37g,12.8mmol)，醋酸铵(29.6g,0.38mol)，醋酸60ml。氮气保护下加热至130℃，反应15小时。反应结束后，冷却，减压除去乙酸，加水，二氯甲烷萃取，收集有机相，干燥并浓缩得粗产品，粗产品用硅胶柱层析纯化得到3.5g，产率70％。
中间体4的合成
合成原料为间溴苯甲醛，合成方法与中间体3一致，产率为65％。
中间体5的合成
在烧瓶中，加入中间体2(6g,25.5mmol)，间溴苯甲醛(4.7g,25.5mmol)，醋酸铵(49g,0.64mol)，醋酸100ml。氮气保护下加热至130℃，反应16小时。反应结束后，冷却，减压除去乙酸，加水，二氯甲烷萃取，收集有机相，干燥并浓缩得粗产品，粗产品用硅胶柱层析纯化得到6g，产率59％。
实施例1-化合物18的合成
圆底烧瓶中装入中间体4(1g,2.5mmol)、2,4-二苯基-6-((3-频哪醇硼酸酯)苯基)-1,3,5-三嗪(1.2g,2.75mmol)、四(三苯基膦)钯(0.29g,0.25mmol)、碳酸钾(0.86g,6.2mmol)、二氧六环/水(10ml/2ml)。反应混合物在氮气气氛下升温至110℃下搅拌10小时。反应结束后，加水洗涤，二氯甲烷萃取，浓缩得粗产品，经硅胶柱层析纯化得1.27g，收率81％。Ms(ESI):629.2(M+1)。
实施例2-化合物21的合成
圆底烧瓶中装入中间体3(1g,2.5mmol)、N-苯基-3-咔唑硼酸(0.79g,2.75mmol)、四(三苯基膦)钯(0.29g,0.25mmol)、碳酸钾(0.86g,6.2mmol)、甲苯/水(10ml/2ml)。反应混合物在氮气气氛下升温至110℃下搅拌8小时。反应结束后，加水洗涤，二氯甲烷萃取，浓缩得粗产品，经硅胶柱层析纯化得1.04g，收率74％。Ms(ESI):563.2(M+1)。
实施例3-化合物29的合成
圆底烧瓶中装入中间体5(2g,5mmol)、(3-(10H-螺[吖啶-9,9'-芴]-10-基)苯基)硼酸(2.47g,6mmol)、四(三苯基膦)钯(0.58g,0.5mmol)、碳酸钾(1.7g,12.5mmol)、二氧六环/水(20ml/4ml)。反应混合物在氮气气氛下升温至110℃下搅拌10小时。反应结束后，
加水洗涤，二氯甲烷萃取，浓缩得粗产品，经硅胶柱层析纯化得3.08g，收率85％。Ms(ESI):728.3(M+1)。玻璃砖转变温度为99℃，图1为化合物29的DSC图谱。
实施例4-6
有机电致发光器件的制备
使用本发明实施例中的化合物制备OLED。
首先，将透明导电ITO玻璃基板110(上面带有阳极120)依次经过：去离子水、乙醇、丙酮、去离子水洗净，再用氧等离子处理30秒。
然后，蒸镀5nm厚的空穴注入层130(HATCN)。
然后，在空穴注入层上蒸镀50nm厚的空穴传输层140(TAPC)。
然后，在空穴传输层上蒸镀10nm厚的实施例化合物掺杂10wt％Pt-1作为发光层150.
然后，在发光层上蒸镀50nm厚的电子传输层160(TmPyPb)。
最后，蒸镀1.2nm厚的LiF作为电子注入层160和100nm厚的Al作为器件阴极180。
所制备的器件(结构示意图见图2)用Photo Reasearch PR650光谱仪测的在电流密度为1000cd/m2时的效率，如表1所示。
比较例1
除了发光层用CBP代替本发明化合物外，其它的跟实施例4一样。
所制备的器件(结构示意图见图2)用Photo Reasearch PR650光谱仪测的在电流密度为1000cd/m2时的效率，如表1所示。
表1
从表1中可以看出，在相同的条件下，应用本发明的基于咪唑[1,5-a][1,8]萘啶化合物制备的有机电致发光器件的效率高于比较例，如上所述，本发明的化合物具有高的稳定性，本发明制备的有机电致发光器件具有高的效率。
器件中所述的结构式如下：
因此，使用本发明的基于咪唑[1,5-a][1,8]萘啶化合物作为主体，可获得比CBP制备的器件更高的器件效率。同等测试条件下，CBP制备的额器件在1000cd/m2时，其电流效率为41.9cd/A，功率效率为29.1lm/W，外量子效率为12.1％；而本发明的实施例化合物制备的器件均可获得优于以上效率的效果。并且，CBP的玻璃化转变温度Tg为62℃，本发明实施例29化合物有更高的玻璃化转变温度Tg(99℃)，玻璃化转变温度更高，器件发光层形态稳定性好，具有更好的应用前景，更符合有机发光二极管对主体材料的要求。
Claims (13)
1.有机电致发光材料，为具有如下结构式I的化合物：
其中Ar选自C6-C30取代或未取代的芳基、C5-C30的取代或未取代的含有一个或多个杂原子的芳基、N-芳基取代的咔唑基、N-芳基取代的茚并咔唑衍生物取代基、二芳胺基、R1-R8取代的二芳胺基及其环状衍生物Cy，Z为C(R9)2、Si(R9)2、O、S、NR9、SO2，其中R1-R9为独立地为氢、氘、卤素、未取代的烷基、卤代的烷基、氘代的烷基、环烷基、未取代的芳基、烷基取代的芳基、烷氧基、氰基、咔唑基、二苯胺基、或者R1-R9独立地与邻近的基团形成5-8元环，
Cy：
L选自亚苯基、亚联苯基、亚萘基；
R选自氢、氘、取代或未取代的C6-C10的芳基、C6-C10的杂芳基。
2.根据权利要求1所述的有机电致发光材料，Ar选自苯基、萘基、联苯基、菲基、蒽基、芳基蒽基、芘基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、吡啶基、嘧啶基、喹啉基、异喹啉基、三嗪基、吡咯基、呋喃基、噻唑基、喹唑啉基、三氮唑基、苯并噻唑基、苯并噻二唑基、1,2,4-三唑基、三苯胺基、芳基咔唑基、N-芳基取代的咔唑基、二苯胺基、吖啶基及吖啶衍生物取代基、吩噁嗪基及其衍生物取代基、吩噻嗪基及其衍生物取代基；R选自氢、苯基、萘基、吡啶基。
3.根据权利要求2所述的有机电致发光材料，其中Ar选自苯基、萘基、联苯基、菲基、蒽基、芳基蒽基、芘基、二苯并呋喃基、二苯并噻吩基、苯并咪唑基、嘧啶基、三嗪基、喹唑啉基、1,2,4-三唑基、N-苯基-咔唑基、二苯胺基、吖啶基及吖啶衍生物取代基。
4.根据权利要求2所述的有机电致发光材料，为具有下列结构式的化合物：
5.根据权利要求4所述的有机电致发光材料，为具有下列结构式的化合物
6.权利要求1-5任一有机电致发光材料的制备方法，包括如下步骤：
(1)提供化合物A，
(2)在碱性条件下，以四(三苯基膦)钯为催化剂，将含有Ar的硼酸化物或含有Ar的频哪醇硼酸酯与化合物A发生反应，得到式(I)化合物，
A:
7.权利要求6所述的制备方法，所述化合物A的制备方法如下：
A)在正丁基锂作用下，2-溴-1,8-二萘啶与R的甲酸酯发生反应得到化合物B，
B)化合物B与溴代L的甲醛化合物CHO-L-Br发生反应制得化合物A。
8.权利要求7所述的制备方法，所述R的甲酸酯为R的甲酸甲酯。
9.权利要求1-5任一所述的有机电致发光材料在有机电致发光器件中的应用。
10.一种有机电致发光器件，该器件包含阳极、阴极和有机层，有机层包含发光层、空穴注入层、空穴传输层、电子注入层及电子传输层中的至少一层，所述的有机层中至少一层含有权利要求1-5任一所述的有机电致发光材料。
11.根据权利要求10所述的有机电致发光器件，其中有机层发光层、空穴注入层、空穴传输层、电子注入层和电子传输层，权利要求1-5任一所述的有机电致发光材料所在的层为发光层。
12.根据权利要求11所述的有机电致发光器件，权利要求1-5任一所述的有机电致发光材料在发光层单独使用或与其它化合物混合使用。
13.根据权利要求10所述的有机电致发光器件，所述有机层的总厚度为1-1000nm，通过真空蒸镀法、分子束蒸镀法、溶于溶剂的浸涂法、棒涂法或者喷墨打印方法制备而得到。
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