技术领域Technical Field
本发明属于发光材料和发光器件技术领域，具体涉及一种四苯基乙烯衍生物以及包含其的有机电致发光器件。The invention belongs to the technical field of luminescent materials and luminescent devices, and particularly relates to a tetraphenylethylene derivative and an organic electroluminescent device containing the same.
背景技术Background Art
一个有机电致发光器件包括阳极、阴极、以及阳极和阴极之间的发光层。此外，还存在具备堆叠层结构的有机电致发光器件，包括诸如空穴注入层、空穴传输层、电子注入层、电子传输层等有机层。An organic electroluminescent device includes an anode, a cathode, and a light-emitting layer between the anode and the cathode. In addition, there are organic electroluminescent devices with a stacked layer structure, including organic layers such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.
当向有机电致发光器件施加电压时，空穴从阳极注入，电子从阴极注入，在发光层中，注入的空穴和电子组合形成激子，激子由激发态回到基态的过程中，能量以光的形式释放出来。When voltage is applied to an organic electroluminescent device, holes are injected from the anode and electrons are injected from the cathode. In the light-emitting layer, the injected holes and electrons combine to form excitons. In the process of the excitons returning from the excited state to the ground state, energy is released in the form of light.
通过在发光层中使用不同的发光材料，可以实现多种颜色的发光。因此，有机电致发光器件被大量应用于显示方面。其中，对三基色红、绿、蓝的材料的研究最为活跃，通过对有机发光材料的改良研究，有机电致发光器件的性能正在慢慢地提升。By using different luminescent materials in the luminescent layer, multiple colors of light can be emitted. Therefore, organic electroluminescent devices are widely used in display. Among them, the research on the materials of the three primary colors of red, green and blue is the most active. Through the improvement of organic luminescent materials, the performance of organic electroluminescent devices is gradually improving.
例如，专利文献1(JP 161218/2019)公开了一种技术，其中蒽基化合物和芘基化合物被用作有机电致发光元件的发光材料，可以实现良好的载流子平衡，从而提高器件效率和器件寿命。For example, Patent Document 1 (JP 161218/2019) discloses a technology in which anthracene-based compounds and pyrene-based compounds are used as light-emitting materials for organic electroluminescent elements, which can achieve good carrier balance and thus improve device efficiency and device life.
另外，为了提高亮度效率和寿命，在专利文献2(EP 3150579B1)中公开了一种用于发光器件的化合物，该化合物具有荧蒽骨架和含电子受体N原子的芳杂环。In addition, in order to improve the brightness efficiency and lifespan, Patent Document 2 (EP 3150579B1) discloses a compound for a light-emitting device, the compound having a fluoranthene skeleton and an aromatic heterocyclic ring containing an electron acceptor N atom.
在专利文献3(US 2019/0013478A1)中，公开了一种具备双极性的p-共轭硼化合物，该化合物作为有机电致发光器件中的荧光化合物，可以符合各种能级，可用于制备发光效率高、高温下可稳定存储的有机电致发光器件。In patent document 3 (US 2019/0013478A1), a bipolar p-conjugated boron compound is disclosed. As a fluorescent compound in an organic electroluminescent device, this compound can conform to various energy levels and can be used to prepare an organic electroluminescent device with high luminous efficiency and stable storage at high temperatures.
尽管器件的发光性能正在不断提升，但是，高性能的器件对材料要求越来越高，有机电致发光领域仍需要开发能够进一步提高器件性能的新材料。Although the luminescence performance of devices is constantly improving, high-performance devices have increasingly higher requirements for materials, and the field of organic electroluminescence still needs to develop new materials that can further improve device performance.
发明内容Summary of the invention
本发明的目的在于提供一种四苯基乙烯衍生物，以及使用其的高发光效率、低开启电压、高色纯度的蓝光发光有机电致发光器件。The object of the present invention is to provide a tetraphenylethylene derivative and a blue light emitting organic electroluminescent device with high luminous efficiency, low turn-on voltage and high color purity using the same.
本发明的目的通过以下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种四苯基乙烯衍生物，结构通式如下所示：A tetraphenylethylene derivative, the general structural formula of which is shown below:
式(1)中，R1～R4各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有3至30个碳原子的取代或未取代的甲硅烷基、具有1至30个碳原子的取代或未取代的烷氧基；In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar2和Ar3各自独立地选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；m和n各自独立地为0或1，当Ar1选自式(2-1)时，m和n至少有一个为1；Ar2 and Ar3 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring carbon atoms; m and n are each independently 0 or 1, and when Ar1 is selected from formula (2-1), at least one of m and n is 1;
Ar1选自如下基团：Ar1 is selected from the following groups:
式(2)中，In formula (2),
式(2-1)中，R11～R12各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；a为1、2或3；In formula (2-1), R11 to R12 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms; a is 1, 2 or 3;
式(2-2)中，In formula (2-2),
R21～R22各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R21 to R22 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar21选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；b为0或1；Ar21 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; b is 0 or 1;
式(2-3)中，In formula (2-3),
R31～R32各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R31 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar31选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；c为0或1；Ar31 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; c is 0 or 1;
式(2-4)中，R41～R42各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；In formula (2-4), R41 to R42 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
式(2-5)中，In formula (2-5),
R51选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R51 is selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar51选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；e为0或1；Ar51 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; e is 0 or 1;
式(2-6)中，In formula (2-6),
R61选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R is selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar61选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；f为0或1；Ar61 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; f is 0 or 1;
X1选自O原子、S原子、NR或C(R)2，R选自氢原子或以下基团：具有1至20个碳原子的取代或未取代的烷基，具有3至30个环碳原子的取代或未取代的环烷基，具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环原子的取代或未取代的杂芳基；X1 is selected from an O atom, an S atom, NR or C(R)2 , and R is selected from a hydrogen atom or the following groups: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms;
式(2-7)中，In formula (2-7),
R71～R72各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R71 to R72 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
X2选自O原子、S原子、NR或C(R)2，R选自氢原子或以下基团：具有1至20个碳原子的取代或未取代的烷基，具有3至30个环碳原子的取代或未取代的环烷基，具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环原子的取代或未取代的杂芳基。X2 is selected from an O atom, an S atom, NR or C(R)2 , and R is selected from a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
优选的，式(1)、式(2)中，Preferably, in formula (1) and formula (2),
所述卤素原子选自氟、氯和溴；The halogen atom is selected from fluorine, chlorine and bromine;
所述具有1至20个碳原子的取代或未取代的烷基中的烷基选自甲基、乙基、正丙基、异丙基、正丁基、s-丁基、异丁基、t-丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、1,1,3,3-四甲基戊基、正己基、1-甲基己基、1,1,3,3,5,5-六甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、正壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、和十八烷基；The alkyl group in the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl;
所述具有2至20个碳原子的取代或未取代的烯基中的烯基选自乙烯基、烯丙基、1-丁烯基、2-丁烯基、3-丁烯基、1,3-丁二烯基、1-甲基乙烯基、1-甲基丙烯基、1,1-二甲基丙烯基，2-甲基丙烯基和1,2-二甲基丙烯基；The alkenyl group in the substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms is selected from vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 1-methylpropenyl, 1,1-dimethylpropenyl, 2-methylpropenyl and 1,2-dimethylpropenyl;
所述具有2至20个碳原子的取代或未取代的炔基中的炔基选自乙炔基、丙炔基和3-戊炔基；The alkynyl group in the substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms is selected from ethynyl, propynyl and 3-pentynyl;
所述具有3至10个环碳原子的取代或未取代的环烷基中的环烷基选自环丙基、环丁基、环戊基、环己基、4-甲基环己基、环辛基、金刚烷基和降冰片基；The cycloalkyl group in the substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, cyclooctyl, adamantyl and norbornyl;
所述具有3至30个碳原子的取代或未取代的甲硅烷基中的甲硅烷基选自三甲基甲硅烷基、三乙基甲硅烷基、三丁基甲硅烷基、二甲基乙基甲硅烷基、叔丁基二甲基甲硅烷基、乙烯基二甲基甲硅烷基、丙基二甲基甲硅烷基、二甲基异丙基甲硅烷基、二甲基丙基甲硅烷基、二甲基丁基甲硅烷基、二甲基叔丁基甲硅烷基、二乙基异丙基甲硅烷基和三异丙基甲硅烷基；The silyl group in the substituted or unsubstituted silyl group having 3 to 30 carbon atoms is selected from trimethylsilyl, triethylsilyl, tributylsilyl, dimethylethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, dimethylisopropylsilyl, dimethylpropylsilyl, dimethylbutylsilyl, dimethyltert-butylsilyl, diethylisopropylsilyl and triisopropylsilyl;
所述具有1至30个碳原子的取代或未取代的烷氧基中的烷氧基选自甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异己氧基、2-丁氧基、叔丁氧基、戊氧基和己氧基。The alkoxy group in the substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms is selected from methoxy, ethoxy, propoxy, isopropoxy, butoxy, isohexyloxy, 2-butoxy, tert-butoxy, pentyloxy and hexyloxy.
所述具有6至30个环碳原子的取代或未取代的芳基中的芳基选自苯基、联苯基、三联苯基、苯并菲基、萘基、蒽基、非那烯基、菲基、芴基、芘基、屈基、螺芴基、苝基和薁基；The aryl group in the substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms is selected from phenyl, biphenyl, terphenyl, triphenylenyl, naphthyl, anthracenyl, phenanthrenyl, phenanthrenyl, fluorenyl, pyrenyl, chrysene, spirofluorenyl, perylenyl and azulenyl;
所述具有5至30个环碳原子的取代或未取代的杂芳基中的杂芳基选自吡咯基、吡啶基、嘧啶基、吡嗪基、吲哚嗪基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、噻吩基、苯并呋喃基、喹啉基、异喹啉基、喹唑啉基、喹恶啉基、苯并咪唑基、二苯并呋喃基、咔唑基和菲咯啉基。The heteroaryl group in the substituted or unsubstituted heteroaryl group having 5 to 30 ring carbon atoms is selected from pyrrolyl, pyridyl, pyrimidinyl, pyrazinyl, indolizinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furanyl, thienyl, benzofuranyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, benzimidazolyl, dibenzofuranyl, carbazolyl and phenanthrolinyl.
优选的，式(2-6)和式(2-7)中，所述具有1至20个碳原子的取代或未取代的烷基中的烷基选自甲基、乙基、正丙基、异丙基、正丁基、s-丁基、异丁基、t-丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、1,1,3,3-四甲基戊基、正己基、1-甲基己基、1,1,3,3,5,5-六甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、2-乙基己基、正壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、和十八烷基；Preferably, in formula (2-6) and formula (2-7), the alkyl group in the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl;
优选的，式(2-6)和式(2-7)中，所述具有3至30个环碳原子的取代或未取代的环烷基中的环烷基选自环丙基、环丁基、环戊基、环己基、4-甲基环己基、环辛基、金刚烷基和降冰片基。Preferably, in formula (2-6) and formula (2-7), the cycloalkyl group in the substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms is selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, cyclooctyl, adamantyl and norbornyl.
式(1)中，优选的，R1和R3为卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有3至30个碳原子的取代或未取代的甲硅烷基、具有1至30个碳原子的取代或未取代的烷氧基；R2和R4为氢原子。In formula (1), preferably,R1 andR3 are halogen atoms, cyano groups, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms;R2 andR4 are hydrogen atoms.
作为其他优选形式，R1～R4为氢原子。In another preferred embodiment, R1 to R4 are hydrogen atoms.
优选的，Ar2和Ar3选自苯基、联苯基、萘基、吡啶基和嘧啶基；Preferably, Ar2 and Ar3 are selected from phenyl, biphenyl, naphthyl, pyridyl and pyrimidyl;
优选的，m和n中一个为0，另一个为1；Preferably, one of m and n is 0 and the other is 1;
更优选的，n为1，m为0。More preferably, n is 1 and m is 0.
式(2)中，优选的，式(2-1)中，R11～R12为氢原子，a为1；In formula (2), preferably, in formula (2-1), R11 to R12 are hydrogen atoms, and a is 1;
式(2-2)中，R21～R22为氢原子，b为0；In formula (2-2), R21 to R22 are hydrogen atoms, and b is 0;
式(2-3)中，R31～R32为氢原子，Ar31选自苯基、萘基和联苯基，c为1；In formula (2-3), R31 to R32 are hydrogen atoms, Ar31 is selected from phenyl, naphthyl and biphenyl, and c is 1;
式(2-4)中，R41～R42为氢原子；In formula (2-4), R41 to R42 are hydrogen atoms;
式(2-5)中，R51为氢原子，Ar51选自苯基、萘基和联苯基，e为1；In formula (2-5), R51 is a hydrogen atom, Ar51 is selected from phenyl, naphthyl and biphenyl, and e is 1;
式(2-6)中，R61为氢原子，X1为C(R)2，f为0；In formula (2-6), R61 is a hydrogen atom, X1 is C(R)2 , and f is 0;
式(2-7)中，R71～R72为氢原子，X2选自O原子或S原子。In formula (2-7), R71 to R72 are hydrogen atoms, and X2 is selected from an O atom or a S atom.
一种有机电致发光器件，包含上述的四苯基乙烯衍生物。An organic electroluminescent device comprises the above tetraphenylethylene derivative.
优选的，所述有机电致发光器件包括阳极、阴极、阳极与阴极之间的有机层，其中至少一个有机层是发光层，所述发光层为四苯基乙烯衍生物或含有四苯基乙烯衍生物的混合物。Preferably, the organic electroluminescent device comprises an anode, a cathode, and an organic layer between the anode and the cathode, wherein at least one organic layer is a light-emitting layer, and the light-emitting layer is a tetraphenylethylene derivative or a mixture containing a tetraphenylethylene derivative.
优选的，所述有机电致发光器件是荧光或磷光的单色发光器件、荧光-磷光混合的白光发光器件、具有单个发光单元的简单型发光器件以及具有两个或多个发光单元的串联型发光器件中的任意一种。Preferably, the organic electroluminescent device is any one of a fluorescent or phosphorescent monochromatic light-emitting device, a fluorescent-phosphorescent mixed white light-emitting device, a simple light-emitting device with a single light-emitting unit, and a tandem light-emitting device with two or more light-emitting units.
优选的，所述有机电致发光器件应用于平面显示器件、异形显示器件、曲面显示器件、柔性显示器件和照明器件。如计算机、电视机的显示器件，打印机、厨房电器和广告面板中的可视显示器件，手机、平板电脑、笔记本电脑和数码相机中的显示器件，公交车和火车上的车辆和目的地显示器，智能手表、眼镜或衣服等可穿戴设备，以及仪器的光源、显示面板或导航灯等。Preferably, the organic electroluminescent device is applied to flat display devices, special-shaped display devices, curved display devices, flexible display devices and lighting devices, such as display devices of computers and televisions, visual display devices in printers, kitchen appliances and advertising panels, display devices in mobile phones, tablet computers, notebook computers and digital cameras, vehicle and destination displays on buses and trains, wearable devices such as smart watches, glasses or clothes, and light sources, display panels or navigation lights of instruments.
本发明的式(I)化合物可用作有机电致发光器件用发光材料，可单独或作为混合物的成分用于器件的发光层。根据本发明，可以提供高发光效率、高色纯度的蓝光发光有机电致发光器件，以及在该有机发光器件的有机薄层中使用的材料。The compound of formula (I) of the present invention can be used as a luminescent material for an organic electroluminescent device, and can be used alone or as a component of a mixture in the luminescent layer of the device. According to the present invention, a blue light emitting organic electroluminescent device with high luminous efficiency and high color purity, and a material used in the organic thin layer of the organic light emitting device can be provided.
本发明具有如下的有益效果：The present invention has the following beneficial effects:
(1)本发明的四苯基乙烯衍生物用作有机电致发光器件的发光层具有高发光效率、低开启电压、高色纯度。(1) The tetraphenylethylene derivative of the present invention is used as the light-emitting layer of an organic electroluminescent device and has high luminous efficiency, low turn-on voltage and high color purity.
(2)本发明的四苯基乙烯衍生物制备方法简单，原料易得，适用于大批量生产。(2) The preparation method of the tetraphenylethylene derivative of the present invention is simple, the raw materials are easily available, and it is suitable for mass production.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明提供的一种有机电致发光器件的结构示意图。FIG. 1 is a schematic diagram of the structure of an organic electroluminescent device provided by the present invention.
具体实施方式DETAILED DESCRIPTION
本发明的四苯基乙烯衍生物由下述式(1)所表示：The tetraphenylethylene derivative of the present invention is represented by the following formula (1):
式(1)中，R1～R4各自独立地选自氢原子、氘原子、卤素原子、氰基，或者具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有3至30个碳原子的取代或未取代的甲硅烷基、具有1至30个碳原子的取代或未取代的烷氧基。In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.
优选上述式(1)中，R1和R3为卤素原子、氰基，或者具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有3至30个碳原子的取代或未取代的甲硅烷基、具有1至30个碳原子的取代或未取代的烷氧基；R2和R4为氢原子。Preferably, in the above formula (1),R1 andR3 are halogen atoms, cyano groups, or substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 10 ring carbon atoms, substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, or substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms; andR2 andR4 are hydrogen atoms.
R1和R3的具有1至20个碳原子的取代或未取代的烷基，优选为碳原子数为1～6的烷基。R1和R3的具有2至20个碳原子的取代或未取代的烯基，优选为碳原子数为2～6的烯基。R1和R3的具有2至20个碳原子的取代或未取代的炔基，优选为碳原子数为2～6的炔基。R1和R3的具有3至10个环碳原子的取代或未取代的环烷基，优选为环碳原子数为3～6的环烷基。R1和R3的具有3至30个碳原子的取代或未取代的甲硅烷基，优选为碳原子数为3～12的甲硅烷基。R1和R3的具有1至30个碳原子的取代或未取代的烷氧基，优选为碳原子数为1～6的烷氧基。The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms represented byR1 andR3 is preferably an alkyl group having 1 to 6 carbon atoms. The substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms represented byR1 andR3 is preferably an alkenyl group having 2 to 6 carbon atoms. The substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms represented byR1 andR3 is preferably an alkynyl group having 2 to 6 carbon atoms. The substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms represented byR1 andR3 is preferably a cycloalkyl group having 3 to 6 ring carbon atoms. The substituted or unsubstituted silyl group having 3 to 30 carbon atoms represented byR1 andR3 is preferably a silyl group having 3 to 12 carbon atoms. The substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms represented byR1 andR3 is preferably an alkoxy group having 1 to 6 carbon atoms.
作为其他优选形式，上述式(1)中，R1～R4为氢原子。As another preferred embodiment, in the above formula (1), R1 to R4 are hydrogen atoms.
Ar2和Ar3各自独立地选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；m和n各自独立地为0或1，当Ar1选自式(2-1)时，m和n至少有一个为1。Ar1选自如下式(2)代表的基团：Ar2 and Ar3 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring carbon atoms; m and n are each independently 0 or 1, and when Ar1 is selected from formula (2-1), at least one of m and n is 1. Ar1 is selected from the group represented by the following formula (2):
式(2-1)中，R11～R12各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；a为1、2或3；In formula (2-1), R11 to R12 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms; a is 1, 2 or 3;
式(2-2)中，In formula (2-2),
R21～R22各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R21 to R22 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar21选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；b为0或1；Ar21 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; b is 0 or 1;
式(2-3)中，In formula (2-3),
R31～R32各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R31 to R32 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar31选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；c为0或1；Ar31 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; c is 0 or 1;
式(2-4)中，R41～R42各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；In formula (2-4), R41 to R42 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
式(2-5)中，In formula (2-5),
R51选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R51 is selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar51选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；e为0或1；Ar51 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; e is 0 or 1;
式(2-6)中，In formula (2-6),
R61选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R is selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
Ar61选自具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环碳原子的取代或未取代的杂芳基；f为0或1；Ar61 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 ring carbon atoms; f is 0 or 1;
X1选自O原子、S原子、NR或C(R)2，R选自氢原子或以下基团：具有1至20个碳原子的取代或未取代的烷基，具有3至30个环碳原子的取代或未取代的环烷基，具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环原子的取代或未取代的杂芳基；X1 is selected from an O atom, an S atom, NR or C(R)2 , and R is selected from a hydrogen atom or the following groups: a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms;
式(2-7)中，In formula (2-7),
R71～R72各自独立地选自氢原子、氘原子、卤素原子、氰基、具有1至20个碳原子的取代或未取代的烷基、具有2至20个碳原子的取代或未取代的烯基、具有2至20个碳原子的取代或未取代的炔基、具有3至10个环碳原子的取代或未取代的环烷基、具有1至30个碳原子的取代或未取代的烷氧基；R71 to R72 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;
X2选自O原子、S原子、NR或C(R)2，R选自氢原子或以下基团：具有1至20个碳原子的取代或未取代的烷基，具有3至30个环碳原子的取代或未取代的环烷基，具有6至30个环碳原子的取代或未取代的芳基，或具有5至30个环原子的取代或未取代的杂芳基。X2 is selected from an O atom, an S atom, NR or C(R)2 , and R is selected from a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
在本说明书中，“环碳原子”是指形成饱和环、不饱和环或芳香环的碳原子。“形成环的原子”是指形成杂环(包括饱和环、不饱和环或芳香环)的碳原子和杂原子。In the present specification, "ring carbon atoms" refer to carbon atoms forming a saturated ring, an unsaturated ring or an aromatic ring. "Atoms forming a ring" refer to carbon atoms and heteroatoms forming a heterocyclic ring (including a saturated ring, an unsaturated ring or an aromatic ring).
此外，作为“取代或未取代...”中的取代基，可以举出如后所述的烷基、取代或未取代的甲硅烷基、烷氧基、芳基、芳氧基、芳烷基、环烷基、杂环基、卤素原子、卤素化烷基、羟基、硝基、氰基、羧基等。In addition, examples of the substituent in "substituted or unsubstituted..." include alkyl groups, substituted or unsubstituted silyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups, cycloalkyl groups, heterocyclic groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, nitro groups, cyano groups, carboxyl groups, etc. as described later.
这里，“未取代”是指一个基团被氢原子取代，本发明的氢原子包括轻氢、氘和氚。Here, "unsubstituted" means that a group is substituted with a hydrogen atom, and the hydrogen atom in the present invention includes light hydrogen, deuterium and tritium.
关于上述式(1)和式(2)中的R1～R4、R11～R12、R21～R22、R31～R32、R41～R42、R51、R61、R71～R72、Ar2、Ar3、Ar21、Ar31、Ar51、Ar61所表示的各基团，以及“取代或未取代...”中的取代基，以下进行详细描述。The groups represented by R1 to R4 , R11 to R12 , R21 to R22 , R 31 to R32 , R41 to R42 , R51 , R61 , R71 to R72 , Ar2 , Ar3 , Ar21 , Ar31 , Ar51 , and Ar61 in the above formulae (1) and (2 ), and the substituents in “substituted or unsubstituted...” are described in detail below.
作为烷基，可以举出甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基、正庚基、正辛基等。上述碳原子的数量优选为1～10，进一步优选1～6。其中，优选甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、正己基。Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6. Among them, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and n-hexyl are preferred.
作为烯基，可以举出乙烯基、烯丙基、1-丁烯基、2-丁烯基、3-丁烯基、1,3-丁二烯基、1-甲基乙烯基、1-甲基烯丙基、1,1-二甲基烯丙基、2-甲基烯丙基、1,2-二甲基烯丙基等。其中，优选乙烯基。Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, and 1,2-dimethylallyl. Among them, vinyl is preferred.
作为炔基，可以举出乙炔基、丙炔基、3-戊炔基等。其中，优选乙炔基。Examples of the alkynyl group include ethynyl, propynyl, and 3-pentynyl. Among them, ethynyl is preferred.
作为环烷基，可以举出环丙基、环丁基、环戊基、环己基、4-甲基环己基、金刚烷基和降冰片基。环碳原子的数量优选为3～10，进一步优选5～8，更优选环碳原子的数量为3～8，特别优选环碳原子的数量为3～6。Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantyl and norbornyl. The number of ring carbon atoms is preferably 3 to 10, more preferably 5 to 8, more preferably 3 to 8, and particularly preferably 3 to 6.
作为甲硅烷基，可以举出三甲基甲硅烷基、三乙基甲硅烷基、叔丁基二甲基甲硅烷基、乙烯基二甲基甲硅烷基、丙基二甲基甲硅烷基、三异丙基甲硅烷基等。Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, and a triisopropylsilyl group.
烷氧基以-OY表示，作为Y的例子，可以举出上述的烷基的例子。烷氧基例如为甲氧基、乙氧基。The alkoxy group is represented by -OY, and the above-mentioned examples of the alkyl group can be given as examples of Y. Examples of the alkoxy group include a methoxy group and an ethoxy group.
作为卤素原子，可以举出氟、氯和溴，优选氟原子。Examples of the halogen atom include fluorine, chlorine and bromine, and a fluorine atom is preferred.
作为芳基，可以举出苯基、1-萘基、2-萘基、3-萘基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、并四苯基、基、苯并[c]菲基、苯并[g]基、苯并菲基、1-芴基、2-芴基、3-芴基、4-芴基、9-芴基、苯并芴基、二苯并芴基、2-联苯基、3-联苯基、4-联苯基、三联苯基、荧蒽基等。Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 3-naphthyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, naphthacene, Benzo[c]phenanthrenyl, benzo[g] fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 9-fluorenyl, benzofluorenyl, dibenzofluorenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, terphenyl, fluoranthenyl and the like.
作为Ar21、Ar31～Ar32和Ar’中记载的芳基，优选环碳原子的数量为6～20，更优选6～12，该芳基优选为苯基、萘基、菲基、芴基、蒽基、基、荧蒽基。特别优选为苯基、萘基、菲基、芴基。The aryl group described in Ar21 , Ar31 to Ar32 and Ar' preferably has 6 to 20 ring carbon atoms, more preferably 6 to 12. The aryl group is preferably phenyl, naphthyl, phenanthrenyl, fluorenyl, anthracenyl, Particularly preferred are phenyl, naphthyl, phenanthryl and fluorenyl.
作为杂芳基，可以举出吡咯基、吡嗪基、吡啶基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、1-二苯并呋喃基、2-二苯并呋喃基、3-二苯并呋喃基、4-二苯并呋喃基、1-二苯并噻吩基、2-二苯并噻吩基、3-二苯并噻吩基、4-二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、1-咔唑基、2-咔唑基、3-咔唑基、9-咔唑基、菲啶基、吖啶基、菲咯琳基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑基、噁二唑基、噻吩基、苯并噻吩基等。Examples of the heteroaryl group include pyrrolyl, pyrazinyl, pyridyl, indolyl, isoindolyl, imidazolyl, furyl, benzofuranyl, isobenzofuranyl, 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl, 4-dibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 9-carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolyl, oxadiazolyl, thienyl, and benzothienyl.
上述杂芳基的形成环的原子数优选为5～20，进一步优选为5～14。优选1-二苯并呋喃基、2-二苯并呋喃基、3-二苯并呋喃基、4-二苯并呋喃基、1-二苯并噻吩基、2-二苯并噻吩基、3-二苯并噻吩基、4-二苯并噻吩基、1-咔唑基、2-咔唑基、3-咔唑基、9-咔唑基、吡啶基、嘧啶基。The number of atoms forming a ring of the heteroaryl group is preferably 5 to 20, more preferably 5 to 14. Preferred are 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl, 4-dibenzothienyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 9-carbazolyl, pyridyl, and pyrimidyl.
作为卤素原子，可以是氟、氯和溴，优选氟原子。四苯基乙烯衍生物的具体实例如下，但不限于此：As the halogen atom, fluorine, chlorine and bromine can be used, preferably a fluorine atom. Specific examples of tetraphenylethylene derivatives are as follows, but are not limited thereto:
本发明中，四苯基乙烯衍生物的合成主要通过一系列熟知的Miyaura硼酸酯化反应及Suzuki-Miyaura偶联反应实现。Miyaura硼酸酯化反应，即在钯催化下，卤代芳烃和联硼酸频那醇酯反应制备芳基硼酸酯的反应(Ishiyama,T.；Murata,M.；Miyaura,N.J.Org.Chem.1995,60,7508-7510)。Suzuki-Miyaura反应通常是在钯催化剂存在和惰性气氛下进行，利用芳基硼酸酯与氯、溴、碘代芳烃或烯烃发生交叉偶联(Miyaura,N.；Suzuki,A.Chem.Rev.1995,95,2457-2483.)。In the present invention, the synthesis of tetraphenylethylene derivatives is mainly achieved by a series of well-known Miyaura borate esterification reactions and Suzuki-Miyaura coupling reactions. Miyaura borate esterification reaction is a reaction in which aryl borate is prepared by reacting aryl halide with biboric acid pinacol ester under palladium catalysis (Ishiyama, T.; Murata, M.; Miyaura, N.J. Org. Chem. 1995, 60, 7508-7510). Suzuki-Miyaura reaction is usually carried out in the presence of a palladium catalyst and an inert atmosphere, using aryl borate to cross-couple with chlorine, bromine, iodine or olefin (Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457-2483.).
具体可以通过以下步骤实现：This can be achieved by following the steps below:
(1)四苯基乙烯二溴化物与芳基硼酸酯通过Suzuki反应实现C-C偶联，得到四苯基乙烯中间体产物1；(1) Tetraphenylethylene dibromide and aryl borate are subjected to C-C coupling via Suzuki reaction to obtain tetraphenylethylene intermediate product 1;
(2)四苯基乙烯中间体产物1进一步硼酸酯化，将剩余的溴转化为硼酸酯，得到四苯基乙烯中间体产物2；(2) the tetraphenylethylene intermediate product 1 is further subjected to boric acid esterification to convert the remaining bromine into boric acid ester to obtain the tetraphenylethylene intermediate product 2;
(3)四苯基乙烯中间体产物2与蒽的溴化物通过Suzuki反应实现C-C偶联，得到四苯基乙烯-蒽连接的中间体产物3；(3) The tetraphenylethylene intermediate product 2 is subjected to C-C coupling with anthracene bromide via Suzuki reaction to obtain the tetraphenylethylene-anthracene-linked intermediate product 3;
(4)四苯基乙烯-蒽连接的中间体产物3与二苯芴或二苯芴衍生物的硼酸酯再次通过Suzuki反应偶联，得到目标物。(4) The tetraphenylethylene-anthracene-linked intermediate product 3 is coupled with dibenzofluorene or the boric acid ester of a dibenzofluorene derivative again via Suzuki reaction to obtain the target compound.
其中，可以根据目标化合物适当地调整合成路线及方法，具体操作及工艺条件通过实施例予以说明。The synthetic route and method can be appropriately adjusted according to the target compound, and the specific operation and process conditions are illustrated by examples.
上述四苯基乙烯衍生物，可以作为有机电致发光器件用发光材料、掺杂材料使用。含有四苯基乙烯衍生物作为掺杂物时，含量没有特殊限制，可以是1wt％或更多，优选含量为1.0～80.0wt％，更优选含量为5.0～20.0wt％。The tetraphenylethylene derivatives can be used as luminescent materials and doping materials for organic electroluminescent devices. When the tetraphenylethylene derivatives are used as dopants, the content is not particularly limited and can be 1wt% or more, preferably 1.0-80.0wt%, and more preferably 5.0-20.0wt%.
本发明的有机电致发光器件，包括阳极、阴极、阳极与阴极之间的有机层，其中至少一个有机层是发光层，并且至少一个有机层含有上述的四苯基乙烯衍生物或作为混合物的组分。The organic electroluminescent device of the present invention comprises an anode, a cathode, and an organic layer between the anode and the cathode, wherein at least one organic layer is a light-emitting layer, and at least one organic layer contains the above tetraphenylethylene derivative or a component of a mixture.
在本发明中提及的有机电致发光器件用材料，可以用于荧光发光单元中的发光层主体材料或者掺杂材料。也可以用于荧光发光单元和磷光发光单元中使用的功能层材料，例如，用作在阳极和发光层之间形成的阳极侧有机薄膜层或在阴极和发光层之间形成的阴极侧有机薄膜层的材料，即用于空穴传输层、空穴注入层、电子传输层、电子注入层、空穴阻挡层和电子阻挡层的材料。The materials for organic electroluminescent devices mentioned in the present invention can be used as the main material or doping material of the light-emitting layer in the fluorescent light-emitting unit. They can also be used as functional layer materials used in fluorescent light-emitting units and phosphorescent light-emitting units, for example, materials used as the anode-side organic thin film layer formed between the anode and the light-emitting layer or the cathode-side organic thin film layer formed between the cathode and the light-emitting layer, that is, materials used for the hole transport layer, hole injection layer, electron transport layer, electron injection layer, hole blocking layer and electron blocking layer.
本发明的有机电致发光器件，可以是荧光或磷光的单色发光器件、荧光-磷光混合的白光发光器件、具有单个发光单元的简单型发光器件、以及具有两个或多个发光单元的串联型发光器件中的任意一种。The organic electroluminescent device of the present invention can be any one of a fluorescent or phosphorescent monochromatic light-emitting device, a fluorescent-phosphorescent mixed white light-emitting device, a simple light-emitting device with a single light-emitting unit, and a tandem light-emitting device with two or more light-emitting units.
作为一种简单的有机电致发光器件的代表性结构，给出器件结构如下：As a representative structure of a simple organic electroluminescent device, the device structure is given as follows:
(1)阳极/发光单元/阴极(1) Anode/light-emitting unit/cathode
上述提到的发光单元可以是包含多层荧光发光层和磷光发光层的叠层结构。在这种情况下，为防止磷光发光层中产生的激子扩散到荧光发光层，可以在发光层之间设置间隔层。The above-mentioned light-emitting unit may be a stacked structure including multiple fluorescent light-emitting layers and phosphorescent light-emitting layers. In this case, in order to prevent the excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer, a spacer layer may be provided between the light-emitting layers.
下面给出发光单元的代表性叠层结构。A representative stacked structure of a light-emitting unit is given below.
(a)空穴传输层/发光层(/电子传输层)(a) Hole transport layer/light-emitting layer (/electron transport layer)
(b)空穴传输层/第一磷光发光层/第二磷光发光层(/电子传输层)(b) Hole transport layer/first phosphorescent light-emitting layer/second phosphorescent light-emitting layer (/electron transport layer)
(c)空穴传输层/磷光发光层/间隔层/荧光发光层(/电子传输层)(c) Hole transport layer/phosphorescent emitting layer/spacer layer/fluorescent emitting layer (/electron transport layer)
(d)空穴传输层/第一磷光发光层/第二磷光发光层/间隔层/荧光发光层(/电子传输层)(d) hole transport layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/spacer layer/fluorescent light emitting layer (/electron transport layer)
(e)空穴传输层/第一磷光发光层/间隔层/第二磷光发光层/间隔层/荧光发光层(/电子传输层)(e) hole transport layer/first phosphorescent emitting layer/spacer layer/second phosphorescent emitting layer/spacer layer/fluorescent emitting layer (/electron transport layer)
(f)空穴传输层/磷光发光层/间隔层/第一荧光发光层/第二荧光发光层(/电子传输层)(f) hole transport layer/phosphorescent emitting layer/spacer layer/first fluorescent emitting layer/second fluorescent emitting layer (/electron transport layer)
(g)空穴传输层/电子阻挡层/发光层(/电子传输层)(g) Hole transport layer/electron blocking layer/light-emitting layer (/electron transport layer)
(h)空穴传输层/发光层/空穴阻挡层(/电子传输层)(h) Hole transport layer/light-emitting layer/hole blocking layer (/electron transport layer)
(i)空穴传输层/荧光发光层/三重态阻挡层(/电子传输层)(i) Hole transport layer/fluorescent emitting layer/triplet blocking layer (/electron transport layer)
上所述的磷光或荧光发光层可以发出不同颜色的光。具体的，在叠层结构(d)中，可以举出如下例子：空穴传输层/第一磷光发光层(红光)/第二磷光发光层(绿光)/间隔层/荧光发光层(蓝光)/电子传输层。The phosphorescent or fluorescent light-emitting layer mentioned above can emit light of different colors. Specifically, in the stacked structure (d), the following examples can be cited: hole transport layer/first phosphorescent light-emitting layer (red light)/second phosphorescent light-emitting layer (green light)/spacer layer/fluorescent light-emitting layer (blue light)/electron transport layer.
在每个发光层和空穴传输层或间隔层之间，可以适当地设置电子阻挡层。在每个发光层和电子传输层之间，可以适当地设置空穴阻挡层。由于提供了电子阻挡层或空穴阻挡层，电子和空穴可以被限制在发光层内，从而可以增加发光层中载流子复合的可能性，从而延长寿命。An electron blocking layer may be appropriately provided between each light-emitting layer and the hole transport layer or the spacer layer. A hole blocking layer may be appropriately provided between each light-emitting layer and the electron transport layer. Since an electron blocking layer or a hole blocking layer is provided, electrons and holes may be confined in the light-emitting layer, thereby increasing the possibility of carrier recombination in the light-emitting layer, thereby extending the lifespan.
作为串联有机电致发光器件的代表性结构，给出器件结构如下：As a representative structure of a tandem organic electroluminescent device, the device structure is given as follows:
(2)阳极/第一发光单元/中间层/第二发光单元/阴极(2) Anode/first light-emitting unit/intermediate layer/second light-emitting unit/cathode
第一发光单元和第二发光单元的分层结构可以选自上述提到的发射单元的代表性叠层结构。The layered structure of the first light emitting unit and the second light emitting unit may be selected from the representative layered structures of the emission units mentioned above.
通常，中间层又称为中间电极、中间导电层、载流子形成层、或电子层，可以通过材料配置实现想第一发光层提供电子并向第二发光层提供空穴。Generally, the intermediate layer is also called an intermediate electrode, an intermediate conductive layer, a carrier-forming layer, or an electronic layer, and can provide electrons to the first light-emitting layer and holes to the second light-emitting layer through material configuration.
本发明的有机电致发光器件的一个例子的结构示意图如图1所示，其中有机电致发光器件包括基板1、阳极2、阴极8和设置在阳极2和阴极8之间的有机薄膜层10(发光单元10)。发光单元10包括包含空穴注入层3、空穴传输层4、发光层5、电子传输层6和电子注入层7。电子阻挡层可以设置在发光层5的阳极2侧，并且空穴阻挡层可以设置在发光层5的阴极8侧。通过这些阻挡层，电子和空穴被限制在发光层5中，以提高发光层5中激子的复合度。A schematic structural diagram of an example of an organic electroluminescent device of the present invention is shown in FIG1 , wherein the organic electroluminescent device comprises a substrate 1, an anode 2, a cathode 8, and an organic thin film layer 10 (light-emitting unit 10) disposed between the anode 2 and the cathode 8. The light-emitting unit 10 comprises a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and an electron injection layer 7. An electron blocking layer may be disposed on the anode 2 side of the light-emitting layer 5, and a hole blocking layer may be disposed on the cathode 8 side of the light-emitting layer 5. Through these blocking layers, electrons and holes are confined in the light-emitting layer 5 to increase the recombination degree of excitons in the light-emitting layer 5.
在本发明中，与荧光掺杂材料结合的宿主称为荧光主体材料，与磷光掺杂材料结合的宿主称为磷光主体材料。因此，荧光主体材料和磷光主体材料不能仅仅通过其分子结构的差异来区分。在本发明中，术语“磷光主体”是指用于构成含有磷光掺杂材料的磷光发光层的材料，并不是指不能用作荧光发光层材料的材料。这同样适用于“荧光主体”。In the present invention, the host combined with the fluorescent dopant material is called the fluorescent host material, and the host combined with the phosphorescent dopant material is called the phosphorescent host material. Therefore, the fluorescent host material and the phosphorescent host material cannot be distinguished only by the difference in their molecular structures. In the present invention, the term "phosphorescent host" refers to a material used to constitute a phosphorescent light-emitting layer containing a phosphorescent dopant material, and does not refer to a material that cannot be used as a fluorescent light-emitting layer material. The same applies to the "fluorescent host".
基板Substrate
本发明的有机电致发光器件形成于透明基板上。作为有机电致发光器件的载体，优选400～700nm波段可见光透过率达到80％的玻璃基板。。玻璃板可以由钠钙玻璃、含钡锶玻璃、铅玻璃、铝硅酸盐玻璃、硼硅酸盐玻璃、硼硅酸盐钡玻璃或石英制成。The organic electroluminescent device of the present invention is formed on a transparent substrate. As a carrier of the organic electroluminescent device, a glass substrate with a visible light transmittance of 80% in the 400-700 nm band is preferred. The glass plate can be made of soda-lime glass, barium-strontium glass, lead glass, aluminosilicate glass, borosilicate glass, borosilicate barium glass or quartz.
阳极anode
作为本发明的有机电致发光器件中的阳极材料，向空穴传输层或发光层注入空穴，具有4.5eV以上的功函数是合适的，可以是铟锡氧化物合金(ITO)、氧化锡(NESA)、氧化铟锌合金、金、银、铂和铜等，但不限于这些。阳极是通过特定方法将阳极材料制成薄膜而形成的，例如气相沉积法或溅射法。当器件从发光层透过阳极出光时，阳极对可见光的透过率优选为10％或更高。阳极的薄层电阻最好是几百Ω/°或更低。阳极的薄膜厚度取决于材料的种类，一般为10nm-1μm，优选100-200nm。As the anode material in the organic electroluminescent device of the present invention, it is suitable to inject holes into the hole transport layer or the light-emitting layer and have a work function of more than 4.5 eV, and it can be indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide alloy, gold, silver, platinum and copper, etc., but not limited to these. The anode is formed by making the anode material into a thin film by a specific method, such as vapor deposition or sputtering. When the device emits light from the light-emitting layer through the anode, the transmittance of the anode to visible light is preferably 10% or higher. The sheet resistance of the anode is preferably several hundred Ω/° or less. The film thickness of the anode depends on the type of material, generally 10nm-1μm, preferably 100-200nm.
阴极cathode
所述阴极将电子注入到电子注入层、电子传输层或发光层，并且优选由具有小功函数的材料形成。用于阴极的材料实例包括但不限于铟、铝、镁、镁铟合金、镁铝合金、铝锂合金、铝钪锂合金和镁银合金。与阳极一样，阴极是通过气相沉积法和溅射法等方法将材料制成薄膜而形成的。The cathode injects electrons into the electron injection layer, the electron transport layer or the light emitting layer, and is preferably formed of a material having a small work function. Examples of materials for the cathode include, but are not limited to, indium, aluminum, magnesium, magnesium-indium alloys, magnesium-aluminum alloys, aluminum-lithium alloys, aluminum-scandium-lithium alloys, and magnesium-silver alloys. Like the anode, the cathode is formed by making a material into a thin film by methods such as vapor deposition and sputtering.
发光层Luminescent layer
发光层是具有发光功能的有机层，当采用掺杂系统时，它包含主体材料和掺杂材料。主体材料的主要功能是促进电子和空穴的复合，并将激子限制在发光层中。掺杂剂材料的功能是使复合产生的激子有效发光。The light-emitting layer is an organic layer with a light-emitting function. When a doping system is adopted, it contains a host material and a dopant material. The main function of the host material is to promote the recombination of electrons and holes and confine the excitons in the light-emitting layer. The function of the dopant material is to make the excitons generated by the recombination emit light efficiently.
为了控制发光层中的载流子平衡，发光层可以制成双主体(主体/共主体)层，例如通过使用电子传输主体和空穴传输主体的组合实现。In order to control the carrier balance in the light-emitting layer, the light-emitting layer can be made into a dual-host (host/co-host) layer, for example, by using a combination of an electron-transporting host and a hole-transporting host.
发光层可以制成双掺杂层，两种或多种具有高量子产率的掺杂材料组合使用，每种掺杂剂材料以其自己的颜色发光。例如，通过使用共沉积主体材料、红光掺杂材料和绿光掺杂材料而形成的发光层，可以获取黄光。The light-emitting layer can be made into a double-doped layer, where two or more doping materials with high quantum yields are used in combination, and each dopant material emits light in its own color. For example, by using a light-emitting layer formed by co-depositing a host material, a red light-emitting dopant material, and a green light-emitting dopant material, yellow light can be obtained.
在含两个或多个发光层的叠层结构中，电子和空穴积聚在发光层之间的界面上，因此，复合区域位于发光层之间的界面上，以提高量子效率。In a stacked structure including two or more light-emitting layers, electrons and holes accumulate at the interface between the light-emitting layers, and thus a recombination zone is located at the interface between the light-emitting layers to improve quantum efficiency.
向发光层注入空穴的难易程度和向发光层注入电子的难易程度可能是不同的。同样，空穴传输能力和电子传输能力分别由发光层中空穴和电子的迁移率表示，彼此可能不同。The ease of injecting holes into the light-emitting layer and the ease of injecting electrons into the light-emitting layer may be different. Likewise, the hole transporting ability and the electron transporting ability are represented by the mobility of holes and electrons in the light-emitting layer, respectively, and may be different from each other.
所述发光层是通过已知方法形成的，例如气相沉积法、旋涂法和LB法等，但不限于此。发光层优选为分子沉积膜。分子沉积膜是通过沉积气化材料或通过使材料在溶液或液体状态下固化而形成的薄膜。分子沉积膜与LB法形成的薄膜(分子堆积膜)可以通过组装结构、高阶结构的差异，以及由于结构差异引起的功能差异来区分。The light-emitting layer is formed by a known method, such as vapor deposition, spin coating, and LB method, but is not limited thereto. The light-emitting layer is preferably a molecular deposition film. The molecular deposition film is a thin film formed by depositing a vaporized material or by solidifying a material in a solution or liquid state. The molecular deposition film and the thin film formed by the LB method (molecular stacking film) can be distinguished by differences in assembly structure, high-order structure, and functional differences caused by structural differences.
发光层的厚度优选为5～50nm，更优选7～50nm，最优选10～50nm。如果小于5nm，则可能难以形成发光层并且颜色可能难以控制。如果超过50nm，驱动电压可能会增加。The thickness of the light-emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If it is less than 5 nm, it may be difficult to form the light-emitting layer and the color may be difficult to control. If it exceeds 50 nm, the driving voltage may increase.
(1)荧光发光层(1) Fluorescent light-emitting layer
荧光发光层通常包括至少一种发光材料和至少一种主体材料。The fluorescent light-emitting layer generally includes at least one light-emitting material and at least one host material.
用于荧光发光层的主体材料通常选自一般主体材料，其最好具有比发光材料更宽的带隙，通过从主体材料到发光材料的能量转移机制实现高效发光。优选荧光主体材料的具体实例是取代或未取代的杂环化合物或取代或未取代的芳烃化合物，例如，寡聚亚苯基衍生物、萘衍生物、芴衍生物、荧蒽衍生物、蒽衍生物、菲衍生物、芘衍生物、苯并菲衍生物、苯并蒽衍生物、屈衍生物、并四苯衍生物、苯并屈衍生物等。The host material used for the fluorescent light-emitting layer is usually selected from general host materials, which preferably have a wider band gap than the light-emitting material, and realize efficient light emission through the energy transfer mechanism from the host material to the light-emitting material. Specific examples of preferred fluorescent host materials are substituted or unsubstituted heterocyclic compounds or substituted or unsubstituted aromatic compounds, for example, oligophenylene derivatives, naphthalene derivatives, fluorene derivatives, fluoranthene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, triphenylene derivatives, benzanthracene derivatives, chrysene derivatives, tetracene derivatives, benzochrysene derivatives, etc.
用于荧光发光层的发光材料通常选自一般的发光材料或荧光染料，其优选具有高吸收系数和高量子效率的材料，以便获得高光效。优选荧光发光材料的具体实例是上述四苯基乙烯衍生物，芳烃衍生物，如寡聚亚苯基衍生物、萘衍生物、芴衍生物、荧蒽衍生物、稠合芴衍生物、蒽衍生物、菲衍生物、芘衍生物、苯并菲衍生物、屈衍生物、并四苯衍生物、苯并屈衍生物等。The luminescent material used for the fluorescent light-emitting layer is usually selected from general luminescent materials or fluorescent dyes, and preferably has a material with high absorption coefficient and high quantum efficiency in order to obtain high light efficiency. Specific examples of preferred fluorescent light-emitting materials are the above-mentioned tetraphenylethylene derivatives, aromatic hydrocarbon derivatives, such as oligophenylene derivatives, naphthalene derivatives, fluorene derivatives, fluoranthene derivatives, fused fluorene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, triphenylene derivatives, chrysene derivatives, tetracene derivatives, benzochrysene derivatives, etc.
(2)磷光发光层(2) Phosphorescent layer
磷光发光层通常包括至少一种发光材料和至少一种主体材料。磷光主体材料是一种化合物，它有效地将磷光掺杂材料的三重态能量限制在发光层中，以使磷光掺杂材料有效地发光。The phosphorescent light-emitting layer generally includes at least one light-emitting material and at least one host material. The phosphorescent host material is a compound that effectively confines the triplet energy of the phosphorescent dopant material in the light-emitting layer so that the phosphorescent dopant material emits light efficiently.
用于磷光发光层的主体材料通常选自已知的磷光主体材料。优选磷光主体材料的具体实例包括含氮杂芳烃，如吲哚衍生物、咔唑衍生物、吡啶衍生物、嘧啶衍生物、三嗪衍生物、喹啉衍生物、异喹啉衍生物、喹唑啉衍生物、氮化二苯并噻吩衍生物、氮化二苯并呋喃衍生物、咪唑衍生物、苯并咪唑衍生物、咪唑吡啶衍生物、苯并咪唑菲啶衍生物、苯并咪唑-苯并咪唑衍生物；含氧或硫的杂芳烃，如噻吩衍生物、呋喃衍生物、苯并噻吩衍生物、苯并呋喃衍生物、二苯并噻吩衍生物、二苯并呋喃衍生物；芳基或杂芳基取代的胺衍生物；金属配合物；芳烃衍生物，如苯衍生物、萘衍生物、菲衍生物、三苯衍生物、芴衍生物，等等。The host material for the phosphorescent light-emitting layer is usually selected from known phosphorescent host materials. Specific examples of preferred phosphorescent host materials include nitrogen-containing heteroaromatic hydrocarbons, such as indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, nitrided dibenzothiophene derivatives, nitrided dibenzofuran derivatives, imidazole derivatives, benzimidazole derivatives, imidazole pyridine derivatives, benzimidazole phenanthridine derivatives, benzimidazole-benzimidazole derivatives; oxygen- or sulfur-containing heteroaromatic hydrocarbons, such as thiophene derivatives, furan derivatives, benzothiophene derivatives, benzofuran derivatives, dibenzothiophene derivatives, dibenzofuran derivatives; aryl or heteroaryl substituted amine derivatives; metal complexes; aromatic hydrocarbon derivatives, such as benzene derivatives, naphthalene derivatives, phenanthrene derivatives, triphenyl derivatives, fluorene derivatives, and the like.
用于磷光发光层的掺杂材料(磷光发光材料)是一种能从三重激发态发射光的化合物。磷光掺杂材料不受限制，只要它能从三重激发态发光即可。磷光掺杂材料优选为有机金属配合物，其含有至少一种选自Ir、Pt、Os、Au、Cu、Re和Ru的金属以及配体。优选配体具有邻位金属化键。为获取高的磷光量子产率和外部量子效率的器件，磷光掺杂材料优选为具有选自Ir、Os和Pt的金属原子的化合物。进一步优选的是金属配合物，例如铱配合物、锇配合物和铂配合物，邻位金属化配合物更优选。其中，铱配合物和铂配合物更优选，邻位金属化铱配合物特别优选。The doping material (phosphorescent luminescent material) used for the phosphorescent light-emitting layer is a compound that can emit light from a triplet excited state. The phosphorescent doping material is not limited as long as it can emit light from a triplet excited state. The phosphorescent doping material is preferably an organic metal complex containing at least one metal selected from Ir, Pt, Os, Au, Cu, Re and Ru and a ligand. The preferred ligand has an ortho-metallated bond. In order to obtain a device with high phosphorescent quantum yield and external quantum efficiency, the phosphorescent doping material is preferably a compound having a metal atom selected from Ir, Os and Pt. Further preferred are metal complexes, such as iridium complexes, osmium complexes and platinum complexes, and ortho-metallated complexes are more preferred. Among them, iridium complexes and platinum complexes are more preferred, and ortho-metallated iridium complexes are particularly preferred.
电子传输层Electron transport layer
电子传输层是设置在发光层和阴极之间的有机层，并将电子从阴极传递到发光层。如果提供两个或多个电子传输层，则在某些情况下，更靠近阴极的有机层可称为电子注入层。电子注入层可以有效地将电子从阴极注入有机层单元。The electron transport layer is an organic layer disposed between the light-emitting layer and the cathode, and transfers electrons from the cathode to the light-emitting layer. If two or more electron transport layers are provided, the organic layer closer to the cathode may be referred to as an electron injection layer in some cases. The electron injection layer can effectively inject electrons from the cathode into the organic layer unit.
在其分子中具有一种或多种杂原子的芳香杂环化合物优选用作电子传输层中使用的电子传输材料，并且特别优选含氮杂环衍生物。此外，含氮杂环衍生物优选为含有6或5元氮杂环的芳环化合物，或含有6或5元氮杂环的稠合芳环化合物。An aromatic heterocyclic compound having one or more heteroatoms in its molecule is preferably used as an electron transport material used in the electron transport layer, and a nitrogen-containing heterocyclic derivative is particularly preferred. In addition, the nitrogen-containing heterocyclic derivative is preferably an aromatic ring compound containing a 6- or 5-membered nitrogen heterocycle, or a condensed aromatic ring compound containing a 6- or 5-membered nitrogen heterocycle.
电子传输层的厚度优选，但不特别限于1～100nm。The thickness of the electron transport layer is preferably, but not particularly limited to, 1 to 100 nm.
可选的电子注入层材料的优选例子，除了含氮杂环衍生物外，还包括无机化合物，如绝缘材料和半导体。含有绝缘材料或半导体的电子注入层可以有效地防止电流的泄漏，以提高电子注入的性能。Preferred examples of optional electron injection layer materials include inorganic compounds such as insulating materials and semiconductors in addition to nitrogen-containing heterocyclic derivatives. The electron injection layer containing insulating materials or semiconductors can effectively prevent current leakage to improve the performance of electron injection.
所述绝缘材料优选为至少一种金属化合物选自碱金属硫族化合物、碱土金属硫族化合物、碱金属卤化物和碱土金属卤化物。上面提到的碱金属硫族化合物等是优选的，因为电子注入层的电子注入性能得到进一步增强。优选的碱金属硫族化合物的实例包括Li2O、K2O、Na2S、Na2Se和Na2O，而优选的碱土金属硫族化合物的实例包括CaO、BaO、SrO、BeO、BaS和CaSe。优选的碱金属卤化物的实例包括LiF、NaF、KF、LiCl、KCl和NaCl。碱土金属卤化物的实例包括氟化物，如CaF2、BaF2、SrF2、MgF2和BeF2，以及氟化物以外的卤化物。The insulating material is preferably at least one metal compound selected from alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. The alkali metal chalcogenides mentioned above are preferred because the electron injection performance of the electron injection layer is further enhanced. Examples of preferred alkali metal chalcogenides includeLi2O ,K2O ,Na2S ,Na2Se andNa2O , while examples of preferred alkaline earth metal chalcogenides include CaO, BaO, SrO, BeO, BaS and CaSe. Examples of preferred alkali metal halides include LiF, NaF, KF, LiCl, KCl and NaCl. Examples of alkaline earth metal halides include fluorides such asCaF2 ,BaF2 ,SrF2 ,MgF2 andBeF2 , and halides other than fluorides.
半导体的实例包括至少含有Ba、Ca、Sr、Yb、Al、Ga、In、Li、Na、Cd、Mg、Si、Ta、Sb和Zn组成的组中的一种元素的氧化物、氮化物或氮氧化物。该半导体可以单独使用或两种或多种组合使用。包含在电子注入层中的无机化合物优选形成微晶或无定形绝缘薄膜。如果电子注入层由这种绝缘薄膜形成，则可以减少像素缺陷(例如黑点)，因为形成了更均匀的薄膜。这种无机化合物的实例包括碱金属硫族化物、碱土金属硫族化物、碱金属卤化物和碱土金属卤化物。Examples of semiconductors include oxides, nitrides or oxynitrides of at least one element in the group consisting of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn. The semiconductor can be used alone or in combination of two or more. The inorganic compound contained in the electron injection layer preferably forms a microcrystalline or amorphous insulating film. If the electron injection layer is formed by such an insulating film, pixel defects (such as black spots) can be reduced because a more uniform film is formed. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides.
当使用绝缘材料或半导体时，该层的厚度优选为约0.1～15nm。When an insulating material or a semiconductor is used, the thickness of the layer is preferably about 0.1 to 15 nm.
空穴传输层Hole transport layer
空穴注入/传输层是在发光层和阳极之间形成的有机层，具有将空穴从阳极传输到发光层的功能。当空穴传输层由两层或多层形成时，在某些情况下，更接近阳极的层可以被定义为空穴注入层。空穴注入层具有将空穴从阳极有效注入有机层单元的功能。The hole injection/transport layer is an organic layer formed between the light-emitting layer and the anode, and has the function of transporting holes from the anode to the light-emitting layer. When the hole transport layer is formed of two or more layers, in some cases, the layer closer to the anode can be defined as the hole injection layer. The hole injection layer has the function of efficiently injecting holes from the anode into the organic layer unit.
该空穴传输层可以制成第一空穴传输层(阳极侧)和第二空穴传输层(阴极侧)的两层结构。The hole transport layer may be made into a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).
空穴传输层的厚度优选为10～200nm，没有特别限制。The thickness of the hole transport layer is preferably 10 to 200 nm, but is not particularly limited.
n/p掺杂n/p doping
空穴传输层和电子传输层的载流子注入特性可以通过用电子供体材料掺杂(n)或用电子受体材料掺杂(p)来控制。The carrier injection characteristics of the hole transport layer and the electron transport layer can be controlled by doping with electron donor materials (n) or with electron acceptor materials (p).
n掺杂的典型例子是掺杂金属的电子传输材料，例如Li和Cs，p掺杂的典型例子是掺杂受体材料的空穴传输材料，例如F4TCNQ(2，3，5，6-四氟-7，7，8，8-四氰基喹二甲烷)。Typical examples of n-doping are electron transport materials doped with metals, such as Li and Cs, and typical examples of p-doping are hole transport materials doped with acceptor materials, such as F4 TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane).
间隔层Spacer
在含多层荧光发光层和磷光发光层叠层结构的有机电致发光器件中，在荧光发光层和磷光发光层之间设置一个空间层，以防止磷光发光层中产生的激子扩散到荧光发光层或控制载流子平衡。该间隔层也可以设置在两个或多个磷光发光层之间。In an organic electroluminescent device having a laminated structure of multiple fluorescent light-emitting layers and phosphorescent light-emitting layers, a spacer layer is provided between the fluorescent light-emitting layer and the phosphorescent light-emitting layer to prevent the excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to control the carrier balance. The spacer layer can also be provided between two or more phosphorescent light-emitting layers.
由于间隔层设置在发光层之间，因此优选使用电子传输能力和空穴传输能力兼具的材料。为了防止三重态能量在相邻磷光发光层中的扩散，用于间隔层的材料三重态能量优选为2.6eV或更高。关于空穴传输层所描述的材料可用作间隔层的材料。Since the spacer layer is disposed between the light-emitting layers, it is preferred to use a material having both electron transport capability and hole transport capability. In order to prevent the diffusion of triplet energy in the adjacent phosphorescent light-emitting layer, the triplet energy of the material used for the spacer layer is preferably 2.6 eV or higher. The materials described for the hole transport layer can be used as the material of the spacer layer.
阻挡层Barrier layer
阻挡层，如电子阻挡层，空穴阻挡层和三重态阻挡层，设置在发光层附近。电子阻挡层是防止电子从发光层扩散到空穴传输层的层。空穴阻挡层是防止空穴从发光层扩散到电子传输层的层。Blocking layers, such as electron blocking layers, hole blocking layers, and triplet blocking layers, are provided near the light-emitting layer. The electron blocking layer is a layer that prevents electrons from diffusing from the light-emitting layer to the hole transport layer. The hole blocking layer is a layer that prevents holes from diffusing from the light-emitting layer to the electron transport layer.
三重态阻挡层可防止在发光层中产生的三重态激子扩散到相邻层，并具有将三重态激子限制在发光层中的功能，从而防止能量在除三重态激子的发光掺杂材料以外的分子上失活，例如，在电子传输层中的分子上。The triplet blocking layer prevents triplet excitons generated in the light-emitting layer from diffusing to adjacent layers and has the function of confining the triplet excitons in the light-emitting layer, thereby preventing energy from being deactivated on molecules other than the light-emitting doping material of the triplet excitons, for example, on molecules in the electron transport layer.
三重态阻挡层的材料优选在0.04～0.5MV/cm的电场强度下电子迁移率为10-6cm2/Vs或更高的材料。有几种方法可以测量有机材料的电子迁移率，例如，飞行时间法。在这里，电子迁移率是指由阻抗谱学确定的电子迁移率。The material of the triplet blocking layer preferably has an electron mobility of 10-6 cm2 /Vs or higher at an electric field strength of 0.04 to 0.5 MV/cm. There are several methods for measuring the electron mobility of organic materials, for example, time of flight. Here, electron mobility refers to the electron mobility determined by impedance spectroscopy.
电子注入层的材料优选在0.04～0.5MV/cm的电场强度下电子迁移率为10-6cm2/Vs或更高的材料。在上述范围内，可以促进电子从阴极到电子传输层的注入，还可以促进电子向相邻阻挡层和发光层的注入，从而能够在较低电压下驱动器件。The material of the electron injection layer preferably has an electron mobility of10-6cm2 /Vs or higher at an electric field strength of 0.04-0.5 MV/cm. Within the above range, the injection of electrons from the cathode to the electron transport layer can be promoted, and the injection of electrons into the adjacent blocking layer and the light-emitting layer can also be promoted, so that the device can be driven at a lower voltage.
本发明还涉及一种包含本发明所述的有机电致发光器件的电子设备。The present invention also relates to an electronic device comprising the organic electroluminescent device of the present invention.
使用本发明的式(I)化合物的有机电致发光装置可用于各种显示器使用的面板模块中。The organic electroluminescent device using the compound of formula (I) of the present invention can be used in a panel module used in various displays.
使用本发明的式(I)化合物的有机电致发光装置可用于电视、移动电话和个人电脑的显示元件；或作为电子设备，如照明设备或类似设备。The organic electroluminescent device using the compound of formula (I) of the present invention can be used as a display element of a television, a mobile phone and a personal computer; or as an electronic device such as a lighting device or the like.
使用本发明的式(I)化合物的OLED(有机电致发光器件)可用于所有使用电致发光的装置。合适的设备优选自固定和移动的视觉显示单元和照明单元。固定视觉显示单元，例如计算机、电视机的视觉显示单元、打印机中的视觉显示单元、厨房电器和广告面板、照明和信息面板。移动视觉显示单元，例如手机、平板电脑、笔记本电脑、数码相机、MP3播放器、车辆和公共汽车和火车上的目的地显示器中的视觉显示单元。可以使用本发明的OLED的其它设备例如键盘、衣物、家具、壁纸等。OLEDs (organic electroluminescent devices) using compounds of formula (I) of the present invention can be used in all devices using electroluminescence. Suitable devices are preferably selected from fixed and mobile visual display units and lighting units. Fixed visual display units, such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, lighting and information panels. Mobile visual display units, such as visual display units in mobile phones, tablet computers, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Other devices that can use the OLED of the present invention are keyboards, clothing, furniture, wallpaper, etc.
以下结合实施例对本发明的技术方案进行更详细的描述，但是本发明的范围并不限于以下实施例。The technical solution of the present invention is described in more detail below in conjunction with embodiments, but the scope of the present invention is not limited to the following embodiments.
合成实施例Synthesis Example
实施例1：化合物1的合成Example 1: Synthesis of Compound 1
(1)中间体1的合成(1) Synthesis of intermediate 1
取中间体a(15.68g，32mmol)，中间体b(8.20g，32mmol)，四三苯基膦钯(1.85g，1.6mmol)，碳酸钾(13.28g，96mmol)于反应瓶中，抽换氮气，加400mL甲苯/乙醇/水(8/1/1)，于110℃反应16h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体1，产率为50％。Intermediate a (15.68 g, 32 mmol), intermediate b (8.20 g, 32 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol), potassium carbonate (13.28 g, 96 mmol) were placed in a reaction flask, nitrogen was replaced, 400 mL of toluene/ethanol/water (8/1/1) was added, the mixture was reacted at 110°C for 16 h, and cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain intermediate 1 with a yield of 50%.
(2)中间体2的合成(2) Synthesis of Intermediate 2
取中间体1(8.6g，16mmol)，中间体c(4.88g，19.2mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯(PdCl2(dppf))(352mg，0.48mmol)，醋酸钾(4.72g，48mmol)于反应瓶中，抽换氮气，加120mL二氧六环，于104℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体2，产率为54％。Intermediate 1 (8.6 g, 16 mmol), intermediate c (4.88 g, 19.2 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (PdCl2 (dppf)) (352 mg, 0.48 mmol), potassium acetate (4.72 g, 48 mmol) were placed in a reaction flask, nitrogen was replaced, 120 mL of dioxane was added, the reaction was carried out at 104°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and filtered to obtain Intermediate 2 with a yield of 54%.
(3)中间体3的合成(3) Synthesis of Intermediate 3
取中间体2(4.68g，8mmol)，中间体d(2.69g，8mmol)，四三苯基膦钯(462mg，0.4mmol)，碳酸钾(3.32g，24mmol)于反应瓶中，抽换氮气，加100mL甲苯/乙醇/水(8/1/1)，于110℃反应14h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体3，产率为49％。Intermediate 2 (4.68 g, 8 mmol), intermediate d (2.69 g, 8 mmol), tetrakistriphenylphosphine palladium (462 mg, 0.4 mmol), potassium carbonate (3.32 g, 24 mmol) were placed in a reaction flask, nitrogen was replaced, 100 mL of toluene/ethanol/water (8/1/1) was added, the mixture was reacted at 110°C for 14 h, and cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain intermediate 3 with a yield of 49%.
(4)化合物1的合成(4) Synthesis of Compound 1
取中间体3(2.50g，3.5mmol)，中间体e(1.87g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物1，产率为47％。Intermediate 3 (2.50 g, 3.5 mmol), intermediate e (1.87 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 1 with a yield of 47%.
实施例2：化合物2的合成Example 2: Synthesis of Compound 2
(1)中间体4的合成(1) Synthesis of intermediate 4
取中间体f(15.68g，32mmol)，中间体g(6.53g，32mmol)，四三苯基膦钯(1.85g，1.6mmol)，碳酸钾(13.28g，96mmol)于反应瓶中，抽换氮气，加400mL甲苯/乙醇/水(8/1/1)，于110℃反应16h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体4，产率为53％。Intermediate f (15.68 g, 32 mmol), intermediate g (6.53 g, 32 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol), potassium carbonate (13.28 g, 96 mmol) were placed in a reaction flask, nitrogen was replaced, 400 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 16 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain intermediate 4 with a yield of 53%.
(2)中间体5的合成(2) Synthesis of Intermediate 5
取中间体4(7.8g，16mmol)，中间体c(4.88g，19.2mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯(PdCl2(dppf))(352mg，0.48mmol)，醋酸钾(4.72g，48mmol)于反应瓶中，抽换氮气，加120mL二氧六环，于104℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体5，产率为50％。Intermediate 4 (7.8 g, 16 mmol), intermediate c (4.88 g, 19.2 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (PdCl2 (dppf)) (352 mg, 0.48 mmol), potassium acetate (4.72 g, 48 mmol) were placed in a reaction flask, nitrogen was replaced, 120 mL of dioxane was added, the reaction was carried out at 104°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and filtered to obtain Intermediate 5 with a yield of 50%.
(3)中间体6的合成(3) Synthesis of intermediate 6
取中间体5(4.30g，8mmol)，中间体d(2.69g，8mmol)，四三苯基膦钯(462mg，0.4mmol)，碳酸钾(3.32g，24mmol)于反应瓶中，抽换氮气，加100mL甲苯/乙醇/水(8/1/1)，于110℃反应14h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体6，产率为51％。Intermediate 5 (4.30 g, 8 mmol), intermediate d (2.69 g, 8 mmol), tetrakistriphenylphosphine palladium (462 mg, 0.4 mmol), potassium carbonate (3.32 g, 24 mmol) were placed in a reaction flask, nitrogen was replaced, 100 mL of toluene/ethanol/water (8/1/1) was added, the mixture was reacted at 110°C for 14 h, and cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain Intermediate 6 with a yield of 51%.
(4)化合物2的合成(4) Synthesis of Compound 2
取中间体6(2.32g，3.5mmol)，中间体h(2.08g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物2，产率为52％。Intermediate 6 (2.32 g, 3.5 mmol), intermediate h (2.08 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 2 with a yield of 52%.
实施例3：化合物3的合成Example 3: Synthesis of Compound 3
(1)中间体7的合成(1) Synthesis of intermediate 7
取中间体j(18.35g，32mmol)，中间体b(8.20g，32mmol)，四三苯基膦钯(1.85g，1.6mmol)，碳酸钾(13.28g，96mmol)于反应瓶中，抽换氮气，加400mL甲苯/乙醇/水(8/1/1)，于110℃反应16h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体7，产率为55％。Intermediate j (18.35 g, 32 mmol), intermediate b (8.20 g, 32 mmol), tetrakistriphenylphosphine palladium (1.85 g, 1.6 mmol), potassium carbonate (13.28 g, 96 mmol) were placed in a reaction flask, nitrogen was replaced, 400 mL of toluene/ethanol/water (8/1/1) was added, the mixture was reacted at 110°C for 16 h, and cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain intermediate 7 with a yield of 55%.
(2)中间体8的合成(2) Synthesis of Intermediate 8
取中间体7(9.20g，16mmol)，中间体c(4.88g，19.2mmol)，[1,1'-双(二苯基膦基)二茂铁]二氯化钯(PdCl2(dppf))(352mg，0.48mmol)，醋酸钾(4.72g，48mmol)于反应瓶中，抽换氮气，加120mL二氧六环，于104℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体8，产率为51％。Intermediate 7 (9.20 g, 16 mmol), intermediate c (4.88 g, 19.2 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (PdCl2 (dppf)) (352 mg, 0.48 mmol), potassium acetate (4.72 g, 48 mmol) were placed in a reaction flask, nitrogen was replaced, 120 mL of dioxane was added, the reaction was carried out at 104°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and column chromatography was performed to obtain Intermediate 8 with a yield of 51%.
(3)中间体9的合成(3) Synthesis of Intermediate 9
取中间体k(3.68g，8mmol)，中间体d(2.69g，8mmol)，四三苯基膦钯(462mg，0.4mmol)，碳酸钾(3.32g，24mmol)于反应瓶中，抽换氮气，加100mL甲苯/乙醇/水(8/1/1)，于110℃反应14h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到中间体9，产率为53％。Intermediate k (3.68 g, 8 mmol), intermediate d (2.69 g, 8 mmol), tetrakistriphenylphosphine palladium (462 mg, 0.4 mmol), potassium carbonate (3.32 g, 24 mmol) were placed in a reaction flask, nitrogen was replaced, 100 mL of toluene/ethanol/water (8/1/1) was added, the mixture was reacted at 110°C for 14 h, and cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by spin drying, and column chromatography was performed to obtain intermediate 9 with a yield of 53%.
(4)化合物3的合成(4) Synthesis of Compound 3
取中间体8(2.48g，4mmol)，中间体9(2.35g，4mmol)，四三苯基膦钯(231mg，0.2mmol)，碳酸钾(1.66g，12mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物3，产率为50％。Intermediate 8 (2.48 g, 4 mmol), intermediate 9 (2.35 g, 4 mmol), tetrakistriphenylphosphine palladium (231 mg, 0.2 mmol), potassium carbonate (1.66 g, 12 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 3 with a yield of 50%.
实施例4：化合物4的合成Example 4: Synthesis of Compound 4
取中间体9(2.06g，3.5mmol)，中间体m(2.08g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物4，产率为52％。Intermediate 9 (2.06 g, 3.5 mmol), intermediate m (2.08 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 4 with a yield of 52%.
实施例5：化合物5的合成Example 5: Synthesis of Compound 5
取中间体9(2.06g，3.5mmol)，中间体n(2.08g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物5，产率为49％。Intermediate 9 (2.06 g, 3.5 mmol), intermediate n (2.08 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 5 with a yield of 49%.
实施例6：化合物6的合成Example 6: Synthesis of Compound 6
取中间体9(2.06g，3.5mmol)，中间体p(2.35g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物6，产率为47％。Intermediate 9 (2.06 g, 3.5 mmol), intermediate p (2.35 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 6 with a yield of 47%.
实施例7：化合物7的合成Example 7: Synthesis of Compound 7
取中间体9(2.06g，3.5mmol)，中间体q(2.24g，4.2mmol)，四三苯基膦钯(202mg，0.175mmol)，碳酸钾(1.45g，10.5mmol)于反应瓶中，抽换氮气，加50mL甲苯/乙醇/水(8/1/1)，于110℃反应10h，冷却至室温。加二氯甲烷，水萃取，收集有机层，旋干，过柱，得到化合物7，产率为49％。Intermediate 9 (2.06 g, 3.5 mmol), intermediate q (2.24 g, 4.2 mmol), tetrakistriphenylphosphine palladium (202 mg, 0.175 mmol), potassium carbonate (1.45 g, 10.5 mmol) were placed in a reaction flask, nitrogen was replaced, 50 mL of toluene/ethanol/water (8/1/1) was added, the reaction was carried out at 110°C for 10 h, and the mixture was cooled to room temperature. Dichloromethane was added, water was extracted, the organic layer was collected, dried by rotation, and passed through a column to obtain compound 7 with a yield of 49%.
应用实施例Application Examples
比较例1Comparative Example 1
在一个尺寸为25×75×1.1mm的玻璃基板上，提供了由氧化铟锡形成的120nm厚的透明电极。这个透明电极作为阳极，经过紫外线臭氧清洗后，将玻璃基片放入真空蒸镀设备中。On a glass substrate with a size of 25×75×1.1mm, a 120nm thick transparent electrode formed of indium tin oxide is provided. This transparent electrode is used as an anode. After ultraviolet ozone cleaning, the glass substrate is placed in a vacuum evaporation device.
首先，沉积一层由HATCN形成的5nm厚的薄膜作为空穴注入层。接着，在其上沉积一层由TAPC形成的25nm厚的薄膜作为空穴传输层。再在TAPC上，蒸镀激子阻挡层TCTA，厚度为15nm。在TCTA之上，蒸镀厚度为20nm的发光层P1。然后，在该发光层上沉积由TPBi形成的40nm厚的薄膜作为电子传输层。最后一步，沉积一层1nm厚的LiF薄膜和一层100nm厚的铝膜，起到阴极的作用。从而得到有机电致发光器件。First, a 5nm thick film formed of HATCN is deposited as a hole injection layer. Then, a 25nm thick film formed of TAPC is deposited thereon as a hole transport layer. Then, on TAPC, an exciton blocking layer TCTA is evaporated with a thickness of 15nm. On top of TCTA, a light-emitting layer P1 with a thickness of 20nm is evaporated. Then, a 40nm thick film formed of TPBi is deposited on the light-emitting layer as an electron transport layer. In the last step, a 1nm thick LiF film and a 100nm thick aluminum film are deposited to act as a cathode. Thus, an organic electroluminescent device is obtained.
器件结构：ITO/HATCN(5nm)/TPAC(25nm)/TCTA(15nm)/P1(20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).Device structure: ITO/HATCN (5nm)/TPAC (25nm)/TCTA (15nm)/P1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm).
应用实施例中使用的化合物如下所示：The compounds used in the application examples are as follows:
对于由此获得的有机电致发光器件，采用以下方法测量了电流密度为10mA/cm2下的器件性能(发光效率)和CIE1931(x，y)色度坐标。器件的详细电致发光性能数据列于表1中。For the organic electroluminescent device thus obtained, the device performance (luminous efficiency) and CIE1931 (x, y) chromaticity coordinates at a current density of 10 mA/cm2 were measured by the following method. The detailed electroluminescent performance data of the device are listed in Table 1.
·亮度：通过分光光度计(CS-2000，Konica Minolta Holdings，Inc.)测量。Brightness: Measured by a spectrophotometer (CS-2000, Konica Minolta Holdings, Inc.).
·电流效率(L/J)：L/J是亮度与电流密度的比值。电流和电压通过SOURCEMEASURE UNIT 236(Keithley Instruments Inc.)测量，亮度通过分光光度计测量。根据电流值和发光面积计算电流密度，进而得到L/J。Current efficiency (L/J): L/J is the ratio of brightness to current density. Current and voltage are measured by SOURCEMEASURE UNIT 236 (Keithley Instruments Inc.), and brightness is measured by a spectrophotometer. The current density is calculated based on the current value and the luminous area, and then L/J is obtained.
·发光效率(lm/W)：通过以下公式获得：Luminous efficiency (lm/W): obtained by the following formula:
·电致发光峰：通过分光光度计(CS-2000，Konica Minolta Holdings，Inc.)测量。· Electroluminescence peak: measured by a spectrophotometer (CS-2000, Konica Minolta Holdings, Inc.).
·CIE1931(x，y)色度坐标：通过分光光度计(CS-2000，Konica MinoltaHoldings，Inc.)测量。CIE1931 (x, y) chromaticity coordinates: measured by a spectrophotometer (CS-2000, Konica Minolta Holdings, Inc.).
应用实施例1-8Application Examples 1-8
有机电致发光器件的制造和测量方式与比较例1相同，实施例1器件结构与比较例1相同，实施例2～8不同之处在于发光层采用的掺杂材料，器件结构如下：The manufacturing and measuring methods of the organic electroluminescent device are the same as those of Comparative Example 1. The device structure of Example 1 is the same as that of Comparative Example 1. The difference between Examples 2 to 8 lies in the doping material used in the light-emitting layer. The device structure is as follows:
ITO/HATCN(5nm)/TPAC(25nm)/TCTA(15nm)/B-Host：B-Dopant(40:2,ITO/HATCN(5nm)/TPAC(25nm)/TCTA(15nm)/B-Host: B-Dopant(40:2,
20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).20nm)/TPBi(40nm)/LiF(1nm)/Al(100nm).
应用实施例中使用的B-Host化合物结构如下所示，使用掺杂材料B-Dopant具体如表1所示。The structure of the B-Host compound used in the application example is shown below, and the doping material B-Dopant used is specifically shown in Table 1.
器件的详细电致发光性能数据示于表1中。The detailed electroluminescent performance data of the device are shown in Table 1.
表1Table 1
从表1中可知，实施例的器件具备开启电压低，蓝光色纯度高的特性，其中，应用实施例1-8蓝光色纯度更高。It can be seen from Table 1 that the devices of the embodiments have the characteristics of low turn-on voltage and high blue light color purity, among which the blue light color purity of application embodiments 1-8 is higher.
由此，本发明所述四苯基乙烯衍生物可以实现低功耗、蓝光色纯度高的显示器设备。Therefore, the tetraphenylethylene derivatives of the present invention can realize a display device with low power consumption and high blue light color purity.
工业应用Industrial Applications
本发明的有机电致发光装置可用作平面发光体，如壁挂式电视的平板显示器、复印机/打印机的背光、或计量仪器的光源、显示面板、标识灯等。The organic electroluminescent device of the present invention can be used as a planar light emitter, such as a flat panel display of a wall-mounted television, a backlight of a copier/printer, or a light source of a measuring instrument, a display panel, a logo lamp, etc.
上文中仅对本发明的几种实施方式和/或实施例进行了详细描述，但本领域技术人员在非实质性脱离本发明的新颖性教导和效果的范围内，可以容易地对这些示例性实施方式和/或实施例进行修改变更。所有这些变更也包含在本发明的范围内。Only several embodiments and/or examples of the present invention have been described in detail above, but those skilled in the art can easily modify and alter these exemplary embodiments and/or examples without substantially departing from the novel teachings and effects of the present invention. All these modifications are also included in the scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310825160.9ACN117105847A (en) | 2023-07-06 | 2023-07-06 | A tetraphenylethylene derivative and an organic electroluminescent device containing the same |
| Application Number | Priority Date | Filing Date | Title |
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| CN202310825160.9ACN117105847A (en) | 2023-07-06 | 2023-07-06 | A tetraphenylethylene derivative and an organic electroluminescent device containing the same |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310825160.9APendingCN117105847A (en) | 2023-07-06 | 2023-07-06 | A tetraphenylethylene derivative and an organic electroluminescent device containing the same |
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| CN117303998A (en)* | 2023-08-18 | 2023-12-29 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | Tetraphenyl ethylene derivative and organic electroluminescent device comprising same |
| CN117326956A (en)* | 2023-08-21 | 2024-01-02 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | A tetraphenylethylene derivative and an organic electroluminescent device containing the same |
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| CN115838319A (en)* | 2022-11-28 | 2023-03-24 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | A tetraphenylethylene derivative and an organic electroluminescent device comprising it |
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| CN115838319A (en)* | 2022-11-28 | 2023-03-24 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | A tetraphenylethylene derivative and an organic electroluminescent device comprising it |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117303998A (en)* | 2023-08-18 | 2023-12-29 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | Tetraphenyl ethylene derivative and organic electroluminescent device comprising same |
| CN117326956A (en)* | 2023-08-21 | 2024-01-02 | 广东省大湾区华南理工大学聚集诱导发光高等研究院 | A tetraphenylethylene derivative and an organic electroluminescent device containing the same |
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