WO2020151500A1

WO2020151500A1 - Organic electroluminescent compound, electroluminescent material and organic electroluminescent device

Info

Publication number: WO2020151500A1
Application number: PCT/CN2020/071186
Authority: WO
Inventors: 崔林松; 张业欣; 林久栋; 陈华
Original assignee: 苏州久显新材料有限公司
Priority date: 2019-01-23
Filing date: 2020-01-09
Publication date: 2020-07-30
Also published as: CN109651174B; CN109651174A

Abstract

Disclosed herein are an organic electroluminescent compound, an electroluminescent material and an organic electroluminescent component. The organic electroluminescent compound has the structure of formula (1). The organic electroluminescent compound disclosed herein can be a fluorescent material exhibiting good properties. The organic electroluminescent device made of the fluorescent material disclosed herein exhibits advantages, such as low driving voltage, high luminescent efficiency, long service life, and highly pure optical chromatography.

Description

有机电致发光化合物、发光材料及有机电致发光器件Organic electroluminescent compound, luminescent material and organic electroluminescent device

技术领域Technical field

本公开涉及有机电致发光化合物、包含该有机电致发光化合物的发光材料以及包含该有机电致发光化合物的有机电致发光器件。The present disclosure relates to an organic electroluminescent compound, a light emitting material containing the organic electroluminescent compound, and an organic electroluminescent device containing the organic electroluminescent compound.

背景技术Background technique

自从1987年柯达公司C.W.Tang等人首次报道以真空蒸镀的方法制备出Alq ₃为发光材料的双层发光器件以来，有机电致发光器件得到了人们极大的关注。经过30多年的发展，有机电致发光在平板显示、照明方面的引用已经进入产业化初级阶段。 Since the Kodak company CWTang et al. reported for the first time in 1987 that a double-layer light-emitting device with Alq ₃ as a light-emitting material was prepared by a vacuum evaporation method, organic electroluminescent devices have received great attention. After more than 30 years of development, the introduction of organic electroluminescence in flat panel displays and lighting has entered the initial stage of industrialization.

有机电致发光器件一般包括由阳极、金属阴极和它们之间夹着的有机层组成。有机层主要有空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层。有机电致发光器件的基本机制涉及电荷的注入、传输、重组以及形成激子以发光。当外部电压施加到有机电致发光装置时，电子和空穴分别从阴极和阳极注入，电子将从阴极注入到最低未占有分子轨道，而空穴将从阳极注入到最高占有分子轨道中。当电子与空穴在发光层中重组时，形成激子并且随后发光。当发光分子吸收能量达到激发态时，根据电子自旋的统计规则，单线态激子和三重态激子以25％:75％的比例生成。由于三重态激子的衰减是自旋禁阻的，荧光电致发光器件的内部量子效率仅为25％。然而，在含有重金属元素的磷光材料中，其分子内具有较强的自旋-轨道耦合，促进单重态与三重态之间的系间窜越，因而获得来自单重态和三重态两者的发光，磷光电致发光器件的内部量子效率可达100％。Organic electroluminescence devices generally consist of an anode, a metal cathode and an organic layer sandwiched between them. The organic layer mainly includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The basic mechanism of organic electroluminescent devices involves the injection, transport, and recombination of charges, and the formation of excitons to emit light. When an external voltage is applied to the organic electroluminescence device, electrons and holes are injected from the cathode and anode, respectively, electrons will be injected from the cathode to the lowest unoccupied molecular orbital, and holes will be injected from the anode to the highest occupied molecular orbital. When electrons and holes recombine in the light-emitting layer, excitons are formed and then emit light. When the light-emitting molecule absorbs energy to an excited state, according to the statistical rules of electron spin, singlet excitons and triplet excitons are generated at a ratio of 25%:75%. Since the decay of the triplet excitons is spin forbidden, the internal quantum efficiency of the fluorescent electroluminescent device is only 25%. However, in phosphorescent materials containing heavy metal elements, there is a strong spin-orbit coupling in the molecule, which promotes the intersystem crossing between the singlet state and the triplet state, thereby obtaining both the singlet state and the triplet state. The internal quantum efficiency of phosphorescent electroluminescent devices can reach 100%.

近年来，安达千波矢教授及其同事研发的一种结合热活化型延迟荧光机制的新型荧光有机发光二器件，通过反向系间窜越机制，将自旋禁阻的三重态激子转化为单重态以获得100％的内部量子效率。因此，磷光和延迟荧光电致发光器件的高效率技术受到了广泛的关注。但磷光以及延迟荧光电致发光器件和荧光电致发光器件相比具有寿命短、色纯度差等缺点，尤其是蓝色磷光和延迟荧光电致发光器件中不仅寿命短、色纯度差，发光效率还不够充分，目前还未达到实用化。另外，目前商业化的荧光发光材料有DPVBi、DSA-ph、二萘蒽等。上述材料由于热稳定差，长时间驱动会引起色纯度降低，导致在面板应用的时候出现色差等问题。因此急需开发一批色纯度、效率、热稳定性方面均能满足要求的新材料。In recent years, Professor Chibaya Adachi and his colleagues have developed a new type of fluorescent organic light-emitting device that combines a thermally activated delayed fluorescence mechanism. Through the reverse intersystem crossing mechanism, the spin-forbidden triplet excitons are converted into The singlet state obtains 100% internal quantum efficiency. Therefore, high-efficiency technologies for phosphorescence and delayed fluorescence electroluminescence devices have received extensive attention. However, phosphorescent and delayed fluorescence electroluminescent devices have short life and poor color purity compared with fluorescent electroluminescent devices. Especially in blue phosphorescent and delayed fluorescence electroluminescent devices, they have short life, poor color purity and luminous efficiency. It is not enough and has not yet reached practicality. In addition, currently commercialized fluorescent light-emitting materials include DPVBi, DSA-ph, dinaphthalene anthracene and so on. Due to the poor thermal stability of the above-mentioned materials, long-term driving will cause the color purity to decrease, resulting in problems such as color difference when the panel is applied. Therefore, it is urgent to develop a batch of new materials that can meet the requirements in terms of color purity, efficiency and thermal stability.

发明内容Summary of the invention

发明要解决的问题The problem to be solved by the invention

基于上述理由，本公开的目的在于解决现有技术问题并且提供一种具有热稳定性、高发光效率、高亮度以及长寿命的有机电致发光器件。Based on the above reasons, the purpose of the present disclosure is to solve the problems of the prior art and provide an organic electroluminescent device with thermal stability, high luminous efficiency, high brightness, and long life.

用于解决问题的方案Solutions to the problem

本公开提供一种有机电致发光化合物，其由下述式(1)表示：The present disclosure provides an organic electroluminescent compound, which is represented by the following formula (1):

在所述式(1)中，In the formula (1),

M表示C(R ¹) ₂或者 M means C(R ¹ ) ₂ or

其中虚线表示来自M的键；The dotted line represents the bond from M;

Z在每次出现时相同或不同，其表示C、CR ¹或者N； Z is the same or different every time it appears, which means C, CR ¹ or N;

A表示具有2至5个环的取代或者未取代的稠合芳环单元，Ar ¹、Ar ²在每次出现时相同或者不同地是具有5至30个芳族环原子并且可以被一个或者多个R ¹取代的芳族或杂芳族环系； A represents a substituted or unsubstituted condensed aromatic ring unit having 2 to 5 rings. Ar ¹ and Ar ² are the same or different each time they have 5 to 30 aromatic ring atoms and may be substituted by one or more A R ¹ substituted aromatic or heteroaromatic ring system;

R ¹在每次出现时相同或不同地是H、D、F、Cl、Br、I、CN、NO ₂、NR ²、OR ²、SR ²、C(＝O)R ²、P(＝O)R ²、Si(R ²) ₃、具有1至20个碳原子的取代或未取代的直链状或支链状的烷基、具有3至20个碳原子的取代或未取代的环状的烷基、具有2至20个碳原子的烯基或者炔基，或者具有5至40个芳族环原子并且在每种情况下可被一个或多个R ²取代的芳族或杂芳族环系；其中所述烷基、烯基或者炔基在每种情况下可被一个或者多个R ²取代，并且其中一个或者多个非相邻的CH ₂基团可被R ²C＝CR ²、C≡C、Si(R ²) ₃、C＝O、C＝NR ²、P(＝O)R ²、SO、SO ₂、NR ²、O、S或CONR ²代替，并且其中一个或者多个氢原子可以被D、F、Cl、Br、I、CN或NO ₂代替； R ¹ is the same or different each time H, D, F, Cl, Br, I, CN, NO ₂ , NR ² , OR ² , SR ² , C(=O)R ² , P(=O ) R ² , Si(R ² ) ₃ , substituted or unsubstituted linear or branched alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cyclic with 3 to 20 carbon atoms Alkyl, alkenyl or alkynyl having 2 to 20 carbon atoms, or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R ² Ring system; wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R ² in each case, and wherein one or more non-adjacent CH ₂ groups may be R ² C=CR ^2. C≡C, Si(R ² ) ₃ , C=O, C=NR ² , P(=O)R ² , SO, SO ₂ , NR ² , O, S or CONR ² instead, and one of them or Multiple hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ;

其中，两个相邻的R ¹或两个相邻的R ²任选地形成单环或多环的脂族、芳族或者杂芳族的环系，所述环系可被一个或者多个R ²取代；并且两个或更多个R ¹可以彼此连接并形成环； Wherein, two adjacent R ¹ or two adjacent R ² optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, and the ring system may be composed of one or more R ^{2 is} substituted; and two or more R ¹ may be connected to each other and form a ring;

R ²在每种情况下相同或不同并且选自H、D、F、CN、具有1至20个碳原子的脂肪族基团、具有5至30个芳族环原子的芳族或杂芳族环系，或具有多环的脂肪族环系，其中一个或多个氢原子可以被D、F、CN取代。 R ² is the same or different in each case and is selected from H, D, F, CN, aliphatic groups having 1 to 20 carbon atoms, aromatic or heteroaromatic groups having 5 to 30 aromatic ring atoms A ring system, or an aliphatic ring system with multiple rings, in which one or more hydrogen atoms can be substituted by D, F, or CN.

根据本公开所述的有机电致发光化合物，其中所述式(1)中的A具有选自下列式所组成的群组中的一种结构：The organic electroluminescent compound according to the present disclosure, wherein A in the formula (1) has a structure selected from the group consisting of the following formulas:

其中R ₂至R ₁₅独立地选自由氢原子、具有1至20个碳原子的取代或未取代的烷基、具有6至30个碳原子的取代或未取代的芳基，以及具有3至30个碳原子的取代或未取代的杂芳族基所组成的群组。 Wherein R ₂ to R _{15 are} independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and groups having 3 to 30 carbon atoms. A group of substituted or unsubstituted heteroaromatic groups with three carbon atoms.

根据本公开所述的有机电致发光化合物，其由下述式(1-1)～式(1-4)中的任一个表示：The organic electroluminescent compound according to the present disclosure is represented by any one of the following formulas (1-1) to (1-4):

其中，Ar ¹、Ar ²、M、Z以及A与式(1)中定义相同。 Among them, Ar ¹ , Ar ² , M, Z, and A are the same as defined in formula (1).

根据本公开所述的有机电致发光化合物，其中，由所述式(1)表示的化合物选自下述化合物：The organic electroluminescent compound according to the present disclosure, wherein the compound represented by the formula (1) is selected from the following compounds:

本公开还提供一种发光材料，其包含根据本公开所述的有机电致发光化合物。The present disclosure also provides a luminescent material, which includes the organic electroluminescent compound according to the present disclosure.

根据本公开所述的发光材料，其为荧光发光客体材料。The light-emitting material according to the present disclosure is a fluorescent light-emitting guest material.

本公开还提供一种有机电致发光器件，其包括：第一电极、与所述第一电极对置而具备的第二电极、以及夹在所述第一电极与所述第二电极之间的至少一个有机层，The present disclosure also provides an organic electroluminescent device, which includes: a first electrode, a second electrode provided opposite to the first electrode, and sandwiched between the first electrode and the second electrode At least one organic layer,

其中所述有机层包含根据本公开所述的有机电致发光化合物。The organic layer includes the organic electroluminescent compound according to the present disclosure.

根据本公开所述的有机电致发光器件，其中，包含所述有机电致发光化合物的有机层为发光层。The organic electroluminescent device according to the present disclosure, wherein the organic layer containing the organic electroluminescent compound is a light emitting layer.

发明的效果Effect of invention

螺双芴分子具有非平面的空间结构，两个芴单体以sp ³杂化的碳原子为中心桥连在一起，得到了正交的三维空间结构，具有优良的热稳定性和成膜性，更重要的是其分子间的空间位阻大，可以有效减少激基缔合物和浓度淬灭等不利因素的产出，因此将其引入到具有电致发光特性的分子中，有利于提高分子的稳定性、色纯度和发光效率等。 The spirobifluorene molecule has a non-planar space structure. Two fluorene monomers are bridged together with sp ³ hybridized carbon atoms as the center to obtain an orthogonal three-dimensional structure with excellent thermal stability and film-forming properties. More importantly, the steric hindrance between molecules is large, which can effectively reduce the output of unfavorable factors such as excimer and concentration quenching. Therefore, introducing it into molecules with electroluminescent properties is beneficial to improve Molecular stability, color purity and luminous efficiency, etc.

本公开的有益效果是，本公开制备的发光材料具有较高的玻璃化转变温度、荧光量子产率、电荷迁移率，可增加有机电致发光器件的效率、寿命以及降低驱动电压和功率消耗。本公开的式(1)化合物作为有机电致发光器件的发光材料(掺杂化合物)，可以使得薄膜状态稳定，耐热性优异。通过使用该化合物，能够制得高效率、高亮度、长寿命、低驱动电压的有机电致发光器件。The beneficial effect of the present disclosure is that the luminescent material prepared by the present disclosure has a higher glass transition temperature, fluorescence quantum yield, and charge mobility, which can increase the efficiency and lifetime of the organic electroluminescent device and reduce the driving voltage and power consumption. The compound of formula (1) of the present disclosure, as a light-emitting material (doping compound) of an organic electroluminescent device, can stabilize the film state and has excellent heat resistance. By using the compound, organic electroluminescent devices with high efficiency, high brightness, long life, and low driving voltage can be prepared.

附图说明Description of the drawings

图1为实施例中OLED3中的发光材料化合物83的紫外吸收光谱(UV-Vis)和室温荧光光谱(PL)；紫外吸收光谱和室温荧光光谱在二氯甲烷的稀溶液(1×10 ^-5mol/L)中测得。 Figure 1 shows the ultraviolet absorption spectrum (UV-Vis) and room temperature fluorescence spectrum (PL) of the luminescent material compound 83 in OLED3 in the embodiment; the ultraviolet absorption spectrum and room temperature fluorescence spectrum in a dilute solution of dichloromethane (1×10 ^-5) mol/L).

图2为实施例中OLED2和OLED3的有机电致发光光谱。Figure 2 shows the organic electroluminescence spectra of OLED2 and OLED3 in the embodiment.

图3是显示实施例和比较例的有机电致发光器件的构造的图。Fig. 3 is a diagram showing the configuration of organic electroluminescent devices of Examples and Comparative Examples.

附图标记说明Description of reference signs

1基板1 substrate

2阳极2 anode

3空穴注入层3 hole injection layer

4空穴传输层I4 Hole Transport Layer I

5空穴传输层II5 Hole Transport Layer II

6电子阻挡层6 electron blocking layer

7发光层7 luminescent layer

8空穴阻挡层8 hole blocking layer

9电子传输层9 electron transport layer

10电子注入层10 electron injection layer

11阴极11 cathode

具体实施方式detailed description

以下，对本公开的实施方式进行详细说明。但是，本公开不受以下实施方式的限定。Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited by the following embodiments.

在整个本说明书中提到的“一实施方案”或“实施方案”或“在另一实施方案中”或“在某些实施方案中”或“在本申请的部分实施方式中”意指在至少一实施方案中包括与该实施方案所述的相关的具体参考要素、结构或特征。因此，在整个说明书中不同位置出现的短语“在一实施方案中”或“在实施方案中”或“在另一实施方案中”或“在某些实施方案中”或“在本申请的部分实施方式中”不必全部指同一实施方案。此外，具体要素、结构或特征可以任何适当的方式在一个或多个实施方案中结合。References to "one embodiment" or "embodiment" or "in another embodiment" or "in certain embodiments" or "in some embodiments of this application" throughout this specification mean that At least one embodiment includes specific reference elements, structures, or features related to the embodiment. Therefore, the phrases "in one embodiment" or "in an embodiment" or "in another embodiment" or "in certain embodiments" or "in part of this application" appearing in various places throughout the specification In the embodiments, "not all refer to the same embodiment. In addition, specific elements, structures, or features may be combined in one or more embodiments in any suitable manner.

除非本申请中另外要求，在整个说明书和其后的权利要求书中，词语“包括(comprise)”及其英文变体例如“包括(comprises)”和“包括(comprising)”应解释为开放式的、含括式的意义，即“包括但不限于”。Unless otherwise required in this application, throughout the specification and the following claims, the word "comprise" and its English variants such as "comprises" and "comprising" shall be interpreted as open-ended The inclusive meaning of "including but not limited to".

应当理解，在本申请说明书和附加的权利要求书中用到的单数形式的冠词“一”(对应于英文“a”、“an”和“the”)包括复数的对象，除非文中另外明确地规定。还应当理解，术语“或”通常以其包括“和/或”的含义而使用，除非文中另外明确地规定。It should be understood that the singular article "一" (corresponding to English "a", "an" and "the") used in the description of this application and the appended claims includes plural objects unless the context clearly indicates otherwise Local regulations. It should also be understood that the term "or" is usually used in its meaning including "and/or", unless the context clearly specifies otherwise.

本公开的有机电致发光化合物由下述式(1)表示：The organic electroluminescent compound of the present disclosure is represented by the following formula (1):

在所述式(1)中，In the formula (1),

M表示C(R ¹) ₂或者 M means C(R ¹ ) ₂ or

其中虚线表示来自M的键；The dotted line represents the bond from M;

作为式(1)中具有2至5个环的稠合芳环单元的例子，具体而言，可列举出联苯、三联苯、四联苯、萘、蒽、苊烯、芴、菲、茚、芘、苝、荧蒽、苯并蒽、苯并菲等。As an example of a condensed aromatic ring unit having 2 to 5 rings in the formula (1), specific examples include biphenyl, terphenyl, tetraphenyl, naphthalene, anthracene, acenaphthylene, fluorene, phenanthrene, indene , Pyrene, perylene, fluoranthene, benzanthracene, triphenylene, etc.

作为稠合芳环单元上的取代基，可以例示如下：As the substituent on the fused aromatic ring unit, the following can be exemplified:

氘原子，Deuterium atom,

氰基，Cyano,

硝基，Nitro,

卤素原子，例如氟原子、氯原子、溴原子或碘原子；Halogen atom, such as fluorine atom, chlorine atom, bromine atom or iodine atom;

具有1至6个碳原子的烷基，例如，甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基或正己基；An alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl Or n-hexyl;

具有1至6个碳原子的烷氧基，例如甲氧基、乙氧基或丙氧基；An alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy or propoxy;

烯基，例如乙烯基或烯丙基；Alkenyl, such as vinyl or allyl;

芳氧基，例如苯氧基或甲苯氧基；Aryloxy, such as phenoxy or tolyloxy;

芳基烷氧基，例如苄氧基或苯乙氧基；Arylalkoxy, such as benzyloxy or phenethoxy;

芳族烃基或稠合多环芳族基，例如苯基、联苯基、三联苯基、萘基、蒽基、菲基、芴基、茚基、芘基、苝基、荧蒽基、苯并[9,10]菲基或螺二芴基；Aromatic hydrocarbon groups or condensed polycyclic aromatic groups, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylene, fluoranthene, benzene And [9,10] phenanthryl or spirobifluorenyl;

芳族杂环基，例如吡啶基、噻吩基、呋喃基、吡咯基、喹啉基、异喹啉基、苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、苯并噁唑基、苯并噻唑基、喹喔啉基、苯并咪唑基、吡唑基、二苯并呋喃基、二苯并噻吩基、氮杂芴基、二氮杂芴基、咔啉基、氮杂螺二芴基或二氮杂螺二芴基；Aromatic heterocyclic groups, such as pyridyl, thienyl, furyl, pyrrolyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzoxazole Group, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, azafluorenyl, diazafluorenyl, carboline, aza Spirobifluorenyl or diazaspirobifluorenyl;

芳基乙烯基，例如苯乙烯基或萘乙烯基；和Aryl vinyl groups, such as styryl or naphthalene vinyl groups; and

酰基，例如乙酰基或苯甲酰基。Acyl, for example acetyl or benzoyl.

由Ar ¹、Ar ²表示的芳族环系可以例示出苯、联苯、三联苯、四联苯、苯乙烯、萘、蒽、苊、菲、芴、茚、芘、苝、荧蒽、苯并[9,10]菲、螺二芴等。 The aromatic ring system represented by Ar ¹ and Ar ² can be exemplified by benzene, biphenyl, terphenyl, tetraphenyl, styrene, naphthalene, anthracene, acenaphthene, phenanthrene, fluorene, indene, pyrene, perylene, fluoranthene, benzene And [9,10] phenanthrene, snail difluorene and so on.

由Ar ¹、Ar ²表示的杂芳族环系可以例示出吡啶、联吡啶、三联吡啶、嘧啶、吡嗪、哒嗪、三嗪、吡咯、吡唑、咪唑、***、噁唑、异噁唑、噻唑、异噻唑、噁二唑、噻二唑、呋喃、噻吩、喹啉、异喹啉、喹喔啉、喹唑啉、萘啶、吲哚、异吲哚、苯并咪唑、苯并***、苯并呋喃、苯并噻吩、苯并噁唑、苯并噁二唑、苯并噻唑、苯并噻二唑、吡啶并吡咯、吡啶并咪唑、吡啶并***、蝶啶、吖啶、吩嗪、菲咯啉、吩噁嗪、吩噻嗪、吩硒嗪、吩碲嗪、吩磷嗪、咔唑、咔啉、二苯并呋喃、二苯并噻吩、呫吨等。 The heteroaromatic ring system represented by Ar ¹ and Ar ² can exemplify pyridine, bipyridine, terpyridine, pyrimidine, pyrazine, pyridazine, triazine, pyrrole, pyrazole, imidazole, triazole, oxazole, isooxazole Azole, thiazole, isothiazole, oxadiazole, thiadiazole, furan, thiophene, quinoline, isoquinoline, quinoxaline, quinazoline, naphthyridine, indole, isoindole, benzimidazole, benzo Triazole, benzofuran, benzothiophene, benzoxazole, benzoxadiazole, benzothiazole, benzothiadiazole, pyridopyrrole, pyridoimidazole, pyridotriazole, pteridine, acridine , Phenazine, phenanthroline, phenoxazine, phenothiazine, phenselazine, phenothrazine, phenphosphorazine, carbazole, carboline, dibenzofuran, dibenzothiophene, xanthene, etc.

作为式(1)的R ¹中具有1至20个碳原子的直链状或支链状的烷基，可以例示出甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、正己基、异己基、正庚基、异庚基、正辛基、异辛基、正壬基、异壬基、正癸基、异癸基、正十一烷基、异十一烷基、正十二烷基、异十二烷基、正十三烷基、异十三烷基、正十四烷基、异十四烷基、正十五烷基、异十五烷基、正十六烷基、异十六烷基、正十七烷基、异十七烷基、正十八烷基、异十八烷基、正十九烷基、异十九烷基、正二十烷基、异二十烷基等。 Examples of the linear or branched alkyl group having 1 to 20 carbon atoms in R ¹ of the formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n Decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, iso Myristyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecanyl, isoheptadecanyl, n-octadecyl, isooctadecyl Alkyl, n-nonadecyl, isonadecanyl, n-eicosyl, isoeicosyl, etc.

作为式(1)的R ¹中具有3至20个碳原子的环状的烷基，可以例示出环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环癸基、环十一烷基、环十二烷基、环十三烷基、环十四烷基、环十五烷基、环十六烷基、环十七烷基、环十八烷基、环十九烷基、环二十烷基、1-金刚烷基、2-金刚烷基等。 As the cyclic alkyl group having 3 to 20 carbon atoms in R ¹ of the formula (1), cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclo Decyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecanyl, cyclooctadecyl , Cyclononadecyl, cycloeicosyl, 1-adamantyl, 2-adamantyl, etc.

作为式(1)的R ¹中具有2至20个碳原子的烯基或者炔基，可以例示出乙烯基、烯丙基、异丙烯基、2-丁烯基、1-戊烯基、2-己烯基、1-庚烯基、1-辛烯基、1-壬烯基、1-癸烯基、1-十一烯基、1-十二烯基、1-十三烯基、1-十四烯基、1-十五烯基、1-十六烯基、1-十七烯基、1-十八烯基、1-十九烯基、1-二十烯基、2-庚烯基、2-甲基-2-己烯基、2-辛烯基、2-乙基己烯基、3-甲基-2-庚烯基、2-壬烯基、2-癸烯基、2-十六烯基、2-十八烯基；乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基、癸炔基、1-十一炔基、1-十二炔基、1-十三炔基、1-十四炔基、1-十五炔基、1-十六炔基、1-十七炔基、1-十八炔基、1-十九炔基、1-二十炔基等。 As the alkenyl or alkynyl group having 2 to 20 carbon atoms in R ¹ of the formula (1), vinyl, allyl, isopropenyl, 2-butenyl, 1-pentenyl, 2 -Hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, 1-octadecenyl, 1-nonadecanyl, 1-eicosenyl, 2 -Heptenyl, 2-methyl-2-hexenyl, 2-octenyl, 2-ethylhexenyl, 3-methyl-2-heptenyl, 2-nonenyl, 2-decenyl Alkenyl, 2-hexadecenyl, 2-octadecenyl; ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decyne Group, 1-undecynyl, 1-dodecynyl, 1-tridecynyl, 1-tetradecynyl, 1-pentadecynyl, 1-hexadecynyl, 1-hexadecynyl , 1-octadecynyl, 1-nonadecynyl, 1-eicosynyl and the like.

作为式(1)的R ¹中具有5至40个芳族环原子的芳族或杂芳族环系，可以例示出与上述由Ar ¹、Ar ²表示的芳族或杂芳族环系相同的例子。 As an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms in R ¹ of formula (1), the same as the above-mentioned aromatic or heteroaromatic ring system represented by Ar ¹ and Ar ² can be exemplified example of.

作为式(1)的R ¹中的取代基，可以例示出与上述稠合芳环单元上的取代基相同的例子。 As the substituent in R ¹ of the formula (1), the same examples as the substituent on the above-mentioned condensed aromatic ring unit can be illustrated.

作为式(1)的R ²中的具有1至20个碳原子的脂肪族基团、具有5至30个芳族环原子的芳族或杂芳族环系，可以例示出与上述R ¹中相同的例子。 As an aliphatic group having 1 to 20 carbon atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in R ² of formula (1), the same as those in the above R ¹ The same example.

作为式(1)的R ²中的具有多环的脂肪族环系，可以例示出脂环族环氧化合物等。 As an aliphatic ring system having a polycyclic ring in R ² of the formula (1), an alicyclic epoxy compound and the like can be exemplified.

作为式(1)的R ²中的取代基，可以例示出与上述R ¹中的取代基相同的例子。 As the substituent in R ² of the formula (1), the same examples as the substituent in R ¹ described above can be illustrated.

优选地，所述式(1)中的A具有选自下列式所组成的群组中的一种结构：Preferably, A in the formula (1) has a structure selected from the group consisting of the following formulas:

作为这里的烷基、芳基和杂芳族基，可以例示出与上述Ar ¹、Ar ²、R ¹、R ²中相同的例子。 As the alkyl group, the aryl group, and the heteroaromatic group here, the same examples as in the above-mentioned Ar ¹ , Ar ² , R ¹ , and R ² can be illustrated.

优选地，本公开的有机电致发光化合物由下述式(1-1)～式(1-4)中的任一个表示：Preferably, the organic electroluminescent compound of the present disclosure is represented by any one of the following formulas (1-1) to (1-4):

优选地，本公开的有机电致发光化合物选自下述化合物，但本公开不限于这些化合物。Preferably, the organic electroluminescent compound of the present disclosure is selected from the following compounds, but the present disclosure is not limited to these compounds.

本公开的有机电致发光化合物的纯化通过利用柱色谱的纯化、利用硅胶、活性炭、活性白土等的吸附纯化、利用溶剂的重结晶、析晶法、升华纯化法等来进行。有机电致发光化合物的鉴定利用质谱、元素分析进行。The purification of the organic electroluminescent compound of the present disclosure is performed by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization using a solvent, crystallization method, sublimation purification method, and the like. The identification of organic electroluminescent compounds is performed by mass spectrometry and elemental analysis.

<发光材料><Luminescent Material>

本公开的发光材料包含上述有机电致发光化合物。The light-emitting material of the present disclosure includes the above-mentioned organic electroluminescent compound.

本公开的发光材料可用于有机电致发光器件中，尤其作为有机电致发光器件的荧光发光客体材料。The luminescent material of the present disclosure can be used in organic electroluminescent devices, especially as a fluorescent light-emitting guest material of organic electroluminescent devices.

<有机电致发光器件><Organic Electroluminescence Device>

本公开的有机电致发光器件包括：第一电极、与第一电极对置而具备的第二电极、以及夹在第一电极与第二电极之间的至少一个有机层，其中有机层包含本公开的有机电致发光化合物。The organic electroluminescence device of the present disclosure includes: a first electrode, a second electrode provided opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the organic layer contains the present Disclosed organic electroluminescent compound.

图3是显示本公开的有机电致发光器件的构造的图。如图3所示，在本公开的有机电致发光器件中，例如，阳极2、空穴注入层3、空穴传输层Ⅰ4、空穴传输层Ⅱ5、电子阻挡层6、发光层7、空穴阻挡层8、电子传输层9、电子注入层10和阴极11依次设置在基板1上。FIG. 3 is a diagram showing the configuration of the organic electroluminescent device of the present disclosure. As shown in FIG. 3, in the organic electroluminescent device of the present disclosure, for example, the anode 2, the hole injection layer 3, the hole transport layer I4, the hole transport layer II5, the electron blocking layer 6, the light emitting layer 7, the air The hole blocking layer 8, the electron transport layer 9, the electron injection layer 10 and the cathode 11 are arranged on the substrate 1 in this order.

本公开的有机电致发光器件不限于这样的结构，例如在该多层结构中，可以省略一些有机层。例如，可以是阳极2与空穴传输层Ⅰ4之间的空穴注入层3、发光层7与电子传输层9之间的空穴阻挡层8、以及电子传输层9与阴极11之间的电子注入层10被省略，并且在基板1上依次设置阳极2、空穴传输层Ⅰ4、发光层7、电子传输层9和阴极11的构型。The organic electroluminescent device of the present disclosure is not limited to such a structure, for example, in the multilayer structure, some organic layers may be omitted. For example, it can be the hole injection layer 3 between the anode 2 and the hole transport layer I4, the hole blocking layer 8 between the light-emitting layer 7 and the electron transport layer 9, and the electrons between the electron transport layer 9 and the cathode 11. The injection layer 10 is omitted, and the configuration of the anode 2, the hole transport layer I4, the light emitting layer 7, the electron transport layer 9 and the cathode 11 are sequentially arranged on the substrate 1.

根据本公开的有机电致发光器件除了上述有机层包含由上述式(1)表示的化合物以外，可以通过本技术领域公知的材料和方法进行制造。另外，在上述有机电致发光器件包含多个有机层的情况下，上述有机层可以由相同的物质或不同的物质形成。The organic electroluminescent device according to the present disclosure can be manufactured by materials and methods known in the art, except that the above-mentioned organic layer contains the compound represented by the above-mentioned formula (1). In addition, in the case where the organic electroluminescence device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

例如，根据本公开的有机电致发光器件可以通过在基板上依次层叠第一电极、有机层和第二电极而制造。此时，可以如下制造：利用溅射法或电子束蒸发法之类的PVD(物理蒸镀法)方法，在基板上蒸镀金属或具有导电性的金属氧化物或它们的合金而形成阳极，然后在该阳极上形成包含空穴注入层、空穴传输层、发光层和电子传输层的有机层，之后在该有机物层上蒸镀可用作阴极的物质。但是，制造方法并不限定于此。For example, the organic electroluminescent device according to the present disclosure may be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. At this time, it can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or their alloy is vapor-deposited on a substrate to form an anode, Then, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and then a substance that can be used as a cathode is vapor-deposited on the organic layer. However, the manufacturing method is not limited to this.

作为一个例子，上述第一电极为阳极，上述第二电极为阴极，或者上述第一电极为阴极，上述第二电极为阳极。As an example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

作为本公开的有机电致发光器件的阳极，可以由公知的电极材料构成。例如使用具有大的功函数的电极材料，如钒、铬、铜、锌、金等金属或它们的合金；如氧化锌、氧化铟、氧化铟锡(ITO)、氧化铟锌(IZO)等金属氧化物；如ZnO:Al或SNO ₂:Sb等金属与氧化物的组合；聚(3-甲基噻吩)、聚[3,4-(亚乙基-1,2-二氧)噻吩](PEDOT)、聚吡咯和聚苯胺等导电性高分子等。这些之中，优选ITO。 As the anode of the organic electroluminescent device of the present disclosure, it may be composed of a known electrode material. For example, use electrode materials with large work functions, such as vanadium, chromium, copper, zinc, gold and other metals or their alloys; such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) and other metals Oxide; such as ZnO: Al or SNO ₂ : Sb and other metal and oxide combinations; poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene]( PEDOT), conductive polymers such as polypyrrole and polyaniline. Among these, ITO is preferable.

作为本公开的有机电致发光器件的空穴注入层，可以使用公知的具有空穴注入性质的材料。例如可列举：以铜酞菁为代表的卟啉化合物、萘二胺衍生物、星型的三苯胺衍生物、分子中具有3个以上三苯胺结构通过单键或不含杂原子的二价基团连接的结构的芳胺化合物等三苯胺三聚体及四聚体、六氰基氮杂苯并菲等受体型杂环化合物、涂布型高分子材料。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。As the hole injection layer of the organic electroluminescence device of the present disclosure, a known material having hole injection properties can be used. Examples include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, and divalent groups with three or more triphenylamine structures in the molecule through single bonds or no heteroatoms Triphenylamine trimers and tetramers such as arylamine compounds with a group-linked structure, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

作为本公开的有机电致发光器件的空穴传输层I和II，可以使用公知的具有空穴传输性的材料。例如可列举：含有间咔唑基苯基的化合物；如N,N’-二苯基-N,N’-二(间甲苯基)联苯胺(TPD)、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)、N,N,N’,N’-四联苯基联苯胺等联苯胺衍生物；1,1-双[(二-4-甲苯基氨基)苯基]环己烷(TAPC)；各种三苯胺三聚体及四聚体；9,9',9”-三苯基-9H,9'H,9”H-3,3':6',3”-三咔唑(Tris-PCz)等。它们可以单独地成膜，也可以以与其它材料一起混合成膜而成的单层的形式来使用，还可以制成单独成膜而成的层彼此的层叠结构、混合成膜而成的层彼此的层叠结构、或者单独成膜而成的层与混合成膜而成的层的层叠结构。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。As the hole transport layers I and II of the organic electroluminescent device of the present disclosure, well-known materials having hole transport properties can be used. Examples include: compounds containing m-carbazolyl phenyl; such as N,N'-diphenyl-N,N'-bis(m-tolyl)benzidine (TPD), N,N'-diphenyl- N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N,N',N'-tetraphenylbenzidine and other benzidines Derivatives; 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9',9”-triphenyl Base-9H,9'H,9"H-3,3':6',3"-Tris-PCz, etc.. They can be formed into a film alone or mixed with other materials to form a film It can be used in the form of a single layer, and it can also be made into a laminated structure of layers formed by separate films, a laminated structure of layers formed by mixed films, or layers formed by separate films and mixed films The laminated structure of the resulting layer. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

此外，空穴注入层或空穴传输层中，也可以使用对于该层中通常使用的材料进一步P掺杂三溴苯胺六氯化锑、轴烯衍生物等而成的物质、其部分结构中具有TPD等联苯胺衍生物的结构的高分子化合物等。In addition, in the hole injection layer or the hole transport layer, it is also possible to use a material obtained by P-doping tribromoaniline antimony hexachloride, axene derivatives, etc., for the materials commonly used in the layer, and its partial structure Polymer compounds having the structure of benzidine derivatives such as TPD.

作为本公开的有机电致发光器件的电子阻挡层，可以使用具有电子阻挡作用的公知化合物形成。例如，可列举出：3,3'-二(N-咔唑基)-1,1'-联苯(mCBP)、4,4’,4”-三(N-咔唑基)三苯胺(TCTA)、9,9-双[4-(咔唑-9-基)苯基]芴、1,3-双(咔唑-9-基)苯(mCP)、2,2-双(4-咔唑-9-基苯基)金刚烷(Ad-Cz)等咔唑衍生物；9-[4-(咔唑-9-基)苯基]-9-[4-(三苯基甲硅烷基)苯基]-9H-芴所代表的具有三苯基甲硅烷基和三芳胺结构的化合物；电子阻挡性高的单胺化合物、各种三苯胺二聚体等具备电子阻挡作用的化合物。它们可以单独地成膜，也可以与其它材料一起混合成膜而成的单层的形式来使用，还可以制成单独成膜而成的层彼此的层叠结构、混合成膜而成的层彼此的层叠结构、或者单独成膜而成的层与混合成膜而成的层的层叠结构。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。As the electron blocking layer of the organic electroluminescent device of the present disclosure, it can be formed using a known compound having an electron blocking effect. For example, 3,3'-bis(N-carbazolyl)-1,1'-biphenyl (mCBP), 4,4',4"-tris(N-carbazolyl) triphenylamine ( TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), 2,2-bis(4- Carbazole derivatives such as carbazole-9-ylphenyl)adamantane (Ad-Cz); 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilane) (Yl)phenyl]-9H-fluorene represented by compounds having triphenylsilyl and triarylamine structures; monoamine compounds with high electron blocking properties, various triphenylamine dimers, and other compounds with electron blocking effects. They can be formed into a film individually, or they can be used in the form of a single layer formed by mixing with other materials, and can also be formed into a laminated structure of layers formed by separate films, or layers formed by mixing and forming films. The laminated structure of, or the laminated structure of the layer formed separately and the layer formed by mixing the film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

作为本公开的有机电致发光器件的发光层，优选使用包含式(1)所示的有机电致发光化合物的发光材料。除此之外，还可以使用以Alq ₃为首的羟基喹啉衍生物的金属络合物等各种金属络合物、具有嘧啶环结构的化合物、蒽衍生物、双苯乙烯基苯衍生物、芘衍生物、噁唑衍生物、聚对亚苯基亚乙烯基衍生物等。 As the light-emitting layer of the organic electroluminescent device of the present disclosure, a light-emitting material containing the organic electroluminescent compound represented by formula (1) is preferably used. In addition, various metal complexes such as metal complexes of quinoline derivatives such as Alq ₃ , compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, Pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, etc.

发光层可以由主体材料和掺杂材料构成。作为主体材料，例如可以使用mCBP、mCP、噻唑衍生物、苯并咪唑衍生物、聚二烷基芴衍生物、具有吲哚环作为稠合环的部分结构的杂环化合物等。The light-emitting layer may be composed of a host material and a dopant material. As the host material, for example, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, heterocyclic compounds having an indole ring as a partial structure of a condensed ring, and the like can be used.

作为掺杂材料，优选使用包含式(1)所示的有机电致发光化合物的发光材料。本公开的有机电致发光化合物的掺杂重量比例优选为0.1～50％，更优选为0.5～20％，特别优选为0.5～8％。As the dopant material, a light-emitting material containing an organic electroluminescent compound represented by formula (1) is preferably used. The doping weight ratio of the organic electroluminescent compound of the present disclosure is preferably 0.1-50%, more preferably 0.5-20%, and particularly preferably 0.5-8%.

掺杂材料除了使用本公开的有机电致发光化合物之外，还可以使用芘衍生物、蒽衍生物、喹吖啶酮、香豆素、红荧烯、苝和它们的衍生物、苯并吡喃衍生物、罗丹明衍生物、氨基苯乙烯基衍生物、螺环双芴衍生物等。它们可以单独地成膜，也可以与其它材料一起混合成膜而成的单层的形式来使用，还可以制成单独成膜而成的层彼此的层叠结构、混合成膜而成的层彼此的层叠结构、或者单独成膜而成的层与混合成膜而成的层的层叠结构。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。In addition to the organic electroluminescent compounds of the present disclosure, the dopant materials can also use pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrene, perylene and their derivatives, benzopyrene Pyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirocyclic bifluorene derivatives, etc. They can be formed into a film individually, or they can be used in the form of a single layer formed by mixing with other materials, and can also be formed into a laminated structure of layers formed by separate films, or layers formed by mixing and forming films. The laminated structure of, or the laminated structure of the layer formed by separate film formation and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

作为本公开的有机电致发光器件的空穴阻挡层，可以使用公知的具有空穴阻挡性的化合物来形成。例如可以使用2,4,6-三(3-苯基)-1,3,5-三嗪(T2T)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBi)、浴铜灵(BCP)等菲咯啉衍生物、铝(III)双(2-甲基-8-羟基喹啉)-4-苯基苯酚盐(BAlq)等喹啉醇衍生物的金属络合物、以及各种稀土类络合物、噁唑衍生物、***衍生物、三嗪衍生物等具有空穴阻挡作用的化合物。它们可以单独地成膜，也可以以与其它材料一起混合成膜而成的单层的形式来使用，也可以制成单独成膜而成的层彼此的层叠结构、混合成膜而成的层彼此的层叠结构、或单独成膜而成的层与混合成膜而成的层的层叠结构。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。As the hole blocking layer of the organic electroluminescent device of the present disclosure, it can be formed using a known compound having hole blocking properties. For example, 2,4,6-tris(3-phenyl)-1,3,5-triazine (T2T), 1,3,5-tris(1-phenyl-1H-benzimidazole-2- Phenanthroline derivatives such as benzene (TPBi) and bath copper spirit (BCP), and quinolines such as aluminum (III) bis(2-methyl-8-hydroxyquinoline)-4-phenylphenolate (BAlq) Metal complexes of alcohol derivatives, and various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, and other compounds having hole blocking effects. They can be formed into a film alone, or they can be used in the form of a single layer formed by mixing with other materials, or they can be formed into a laminated structure of layers formed separately, or a layer formed by mixing. The laminated structure of each other, or the laminated structure of the layer formed by separate film formation, and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

上述具有空穴阻挡性的材料也可以用于下述的电子传输层的形成。即，通过使用上述公知的具有空穴阻挡性的材料，可以形成同时作为空穴阻挡层和电子传输层的层。The material having hole blocking properties described above can also be used for the formation of the electron transport layer described below. That is, by using the above-mentioned well-known material having hole blocking properties, it is possible to form a layer that serves as both a hole blocking layer and an electron transport layer.

作为本公开的有机电致发光器件的电子传输层，使用公知的具有电子传输性的化合物形成。例如可以使用Alq ₃、BAlq为首的羟基喹啉衍生物的金属络合物；各种金属络合物；***衍生物；三嗪衍生物；噁二唑衍生物；吡啶衍生物；双(10-羟基苯并[H]喹啉)铍(Be(bq ₂))；如2-[4-(9,10-二萘-2-蒽-2-基)苯基]-1-苯基-1H-苯并咪唑(ZADN)等苯并咪唑衍生物；噻二唑衍生物；蒽衍生物；碳二亚胺衍生物；喹喔啉衍生物；吡啶并吲哚衍生物；菲咯啉衍生物；噻咯衍生物等。它们可以单独地成膜，也可以以与其它材料一起混合成膜而成的单层的形式来使用，也可以制成单独成膜而成的层彼此的层叠结构、混合成膜而成的层彼此的层叠结构、或单独成膜而成的层与混合成膜而成的层的层叠结构。这些材料可以通过蒸镀法、以及旋涂法、喷墨法等公知方法来形成薄膜。 As the electron transport layer of the organic electroluminescence device of the present disclosure, a known compound having electron transport properties is used. For example, metal complexes of quinoline derivatives headed by Alq ₃ and BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; bis(10 -Hydroxybenzo[H]quinoline)beryllium (Be(bq ₂ )); such as 2-[4-(9,10-dinaphthalene-2-anthracene-2-yl)phenyl]-1-phenyl- Benzimidazole derivatives such as 1H-benzimidazole (ZADN); thiadiazole derivatives; anthracene derivatives; carbodiimide derivatives; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives ; Silole derivatives and so on. They can be formed into a film alone, or they can be used in the form of a single layer formed by mixing with other materials, or they can be formed into a laminated structure of layers formed separately, or a layer formed by mixing. The laminated structure of each other, or the laminated structure of the layer formed by separate film formation, and the layer formed by mixing film. These materials can be formed into thin films by well-known methods such as vapor deposition, spin coating, and inkjet.

作为本公开的有机电致发光器件的电子注入层，可以使用本身公知的材料形成。例如可以使用氟化锂、氟化铯等碱金属盐；氟化镁等碱土金属盐；羟基喹啉锂等羟基喹啉衍生物的金属络合物；氧化铝等金属氧化物等。As the electron injection layer of the organic electroluminescence device of the present disclosure, it can be formed using a material known per se. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolate; metal oxides such as alumina.

在电子注入层或电子传输层中，对于该层中通常使用的材料，可以使用进而N掺杂铯等金属、三芳基氧化膦衍生物等而成的材料。In the electron injection layer or the electron transport layer, as the material generally used in the layer, a material obtained by further N-doping metals such as cesium, triarylphosphine oxide derivatives, and the like can be used.

作为本公开的有机电致发光器件的阴极，优选使用具有低功函数的电极材料如铝、镁，或者具有低功函数的合金如镁银合金、镁铟合金、铝镁合金作为电极材料。As the cathode of the organic electroluminescence device of the present disclosure, it is preferable to use an electrode material having a low work function such as aluminum and magnesium, or an alloy having a low work function such as magnesium silver alloy, magnesium indium alloy, and aluminum magnesium alloy as the electrode material.

作为本公开的基板，可以使用传统的有机发光器件中的基板，例如玻璃或塑料。在本公开中，选用玻璃基板。As the substrate of the present disclosure, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In this disclosure, a glass substrate is selected.

实施例Example

在以下实施例中对由上述式(1)表示的化合物及包含其的有机电致发光器件的制造进行具体说明。但是，下述实施例仅用于对本公开进行例示，本公开的范围不限于此。In the following examples, the production of the compound represented by the above formula (1) and the organic electroluminescence device containing the compound will be specifically described. However, the following embodiments are only used to illustrate the present disclosure, and the scope of the present disclosure is not limited thereto.

制备例1：Preparation Example 1:

本制备例用于制备化合物44，其结构式及合成路线如下图所示：This preparation example is used to prepare compound 44, and its structural formula and synthetic route are shown in the figure below:

中间体44A的合成Synthesis of intermediate 44A

在250mL Schlenk瓶中，加入4-溴-9,9'-螺双芴10.19g(25.77mmol)，苯胺3.00g(15.00mmol)，醋酸钯0.36g(1.6mmol)，三叔丁基膦四氟硼酸盐0.93g(3.22mmol)，叔丁醇钠9.29g(96.64mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用100mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用30mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝3:1(V/V))，蒸去溶剂，干燥后，得到9.70g白色固体，收率为73.9％。MS(EI):m/z 407.541[M+].Anal.calcd for C ₃₁H ₂₁N(％):C,91.37；H,5.19；N,3.44；found:C,91.26；H,5.27；N,3.47。 In a 250mL Schlenk bottle, add 10.19g (25.77mmol) of 4-bromo-9,9'-spirobisfluorene, 3.00g (15.00mmol) of aniline, 0.36g (1.6mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.93 g (3.22 mmol) of borate, 9.29 g (96.64 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was stirred at reflux for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 30 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether:dichloromethane=3:1 (V/V)), the solvent is evaporated, and after drying, 9.70 g of white solid is obtained, with a yield of 73.9%. MS(EI): m/z 407.541[M+]. Anal.calcd for C ₃₁ H ₂₁ N(%): C,91.37; H,5.19; N,3.44; found: C,91.26; H,5.27; N, 3.47.

化合物44的合成Synthesis of compound 44

在250mL Schlenk瓶中，加入中间体44A 5.00g(12.27mmol)，9,10-二溴蒽1.65g(4.91mmol)，三(二亚苄基丙酮)二钯0.22g(0.25mmol)，三叔丁基膦四氟硼酸盐0.14g(0.49mmol)，叔丁醇钠2.36g(24.54mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用200mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝2.5:1(V/V))，蒸去溶剂，干燥后，得到3.20g白色结晶，收率为65.9％。MS(EI):m/z 988.47[M+].Anal.calcd for C ₇₆H ₄₈N ₂(％):C,92.28；H,4.89；N,2.83；found:C,92.15；H,4.87；N,2.98。 In a 250mL Schlenk bottle, add intermediate 44A 5.00g (12.27mmol), 9,10-dibromoanthracene 1.65g (4.91mmol), tris(dibenzylideneacetone)dipalladium 0.22g (0.25mmol), tert 0.14 g (0.49 mmol) of butylphosphine tetrafluoroborate, 2.36 g (24.54 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, reflux and stir for 12 hours, and the reaction is complete. Evaporate the solvent, dissolve the residue with 200 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane=2.5:1 (V/V)), the solvent is evaporated, and after drying, 3.20 g of white crystals are obtained, with a yield of 65.9%. MS(EI): m/z 988.47[M+]. Anal.calcd for C ₇₆ H ₄₈ N ₂ (%): C, 92.28; H, 4.89; N, 2.83; found: C, 92.15; H, 4.87; N ,2.98.

制备例2：Preparation Example 2:

本制备例用于制备化合物74，其结构式及合成路线如下图所示：This preparation example is used to prepare compound 74, and its structural formula and synthetic route are shown in the figure below:

中间体74A的合成Synthesis of intermediate 74A

在250mL Schlenk瓶中，加入9,9-二甲基-2-溴芴7.04g(25.77mmol)，苯胺3.00g(32.21mmol)，醋酸钯0.36g(1.61mmol)，三叔丁基膦四氟硼酸盐0.93g(3.22mmol)，叔丁醇钠9.29g(96.64mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用150mL二氯甲烷和100mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝4:1(V/V))，蒸去溶剂，干燥后，得到6.20g白色结晶，收率为67.44％。MS(EI):m/z 285.34[M+].Anal.calcd for C ₂₁H ₁₉N(％):C,88.38；H,6.71；N,4.91；found:C,88.35；H,6.68；N,4.97。 In a 250mL Schlenk bottle, add 7.04g (25.77mmol) of 9,9-dimethyl-2-bromofluorene, 3.00g (32.21mmol) of aniline, 0.36g (1.61mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.93 g (3.22 mmol) of borate, 9.29 g (96.64 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was stirred at reflux for 12 hours, and the reaction was completed. The solvent was evaporated, the residue was dissolved with 150 mL of dichloromethane and 100 mL of water, washed with water, and the organic layer was separated. The aqueous layer was extracted twice with 15 mL of dichloromethane. The organic layers were combined and the solvent was evaporated. The residue was separated by column chromatography. (The silica gel is 350 mesh, and the eluent is petroleum ether:dichloromethane=4:1 (V/V)), the solvent is evaporated, and after drying, 6.20 g of white crystals are obtained, with a yield of 67.44%. MS(EI): m/z 285.34[M+]. Anal.calcd for C ₂₁ H ₁₉ N(%): C,88.38; H,6.71; N,4.91; found: C,88.35; H,6.68; N, 4.97.

化合物74的合成Synthesis of compound 74

在250mL Schlenk瓶中，加入中间体74A 5.00g(17.52mmol)，1,6-二异丙基-3,8-二溴芘3.11g(7.01mmol)，三(二亚苄基丙酮)二钯0.32g(0.35mmol)，三叔丁基膦四氟硼酸盐0.20g(0.70mmol)，叔丁醇钠3.37g(35.04mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用150mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝3:1(V/V))，蒸去溶剂，干燥后，得到3.60g白色结晶，收率为60.2％。MS(EI):m/z 852.68[M+].Anal.calcd for C ₆₄H ₅₆N ₂(％):C,90.10；H,6.62；N,3.28；found:C,90.24；H,6.57；N,3.19。 In a 250mL Schlenk bottle, add intermediate 74A 5.00g (17.52mmol), 1,6-diisopropyl-3,8-dibromopyrene 3.11g (7.01mmol), tris(dibenzylideneacetone)dipalladium 0.32g (0.35mmol), 0.20g (0.70mmol) of tri-tert-butylphosphine tetrafluoroborate, 3.37g (35.04mmol) of sodium tert-butoxide, 150mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.60 g of white crystals are obtained, with a yield of 60.2%. MS(EI): m/z 852.68[M+]. Anal.calcd for C ₆₄ H ₅₆ N ₂ (%): C, 90.10; H, 6.62; N, 3.28; found: C, 90.24; H, 6.57; N , 3.19.

制备例3：Preparation Example 3:

本制备例用于制备化合物83，其结构式及合成路线如下图所示：This preparation example is used to prepare compound 83, and its structural formula and synthetic route are shown in the following figure:

中间体83A的合成Synthesis of Intermediate 83A

在250mL Schlenk瓶中，加入3-溴-9,9'-螺双芴5.90g(14.93mmol)，苯胺2.00g(18.66mmol)，醋酸钯0.21g(0.09 mmol)，三叔丁基膦四氟硼酸盐0.54g(1.87mmol)，叔丁醇钠5.38g(56.0mmol)，甲苯120mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用200mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝2:1(V/V))，蒸去溶剂，干燥后，得到6.40g白色结晶，收率为81.3％。MS(EI):m/z 407.61[M+].Anal.calcd for C ₃₁H ₂₁N(％):C,91.37；H,5.19；N,3.44；found:C,91.31,H,5.23；N,3.46。 In a 250mL Schlenk bottle, add 5.90g (14.93mmol) of 3-bromo-9,9'-spirobisfluorene, 2.00g (18.66mmol) of aniline, 0.21g (0.09mmol) of palladium acetate, and tri-tert-butylphosphine tetrafluoroethylene 0.54 g (1.87 mmol) of borate, 5.38 g (56.0 mmol) of sodium tert-butoxide, 120 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 200 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, and the eluent is petroleum ether: dichloromethane = 2:1 (V/V)), the solvent is evaporated, and after drying, 6.40 g of white crystals are obtained with a yield of 81.3%. MS(EI): m/z 407.61[M+].Anal.calcd for C ₃₁ H ₂₁ N(%): C,91.37; H,5.19; N,3.44; found: C,91.31,H,5.23; N, 3.46.

化合物83的合成Synthesis of compound 83

在250mL Schlenk瓶中，加入中间体83A 2.00g(4.74mmol)，1,6-二异丙基-3,8-二溴芘1.00g(2.06mmol)，三(二亚苄基丙酮)二钯0.09g(0.1mmol)，三叔丁基膦四氟硼酸盐0.06g(0.2mmol)，叔丁醇钠0.99g(10.31mmol)，甲苯100mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用100mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝3:1(V/V))，蒸去溶剂，干燥后，得到1.55g白色结晶，收率为66.76％。MS(EI):m/z 1096.75[M+].Anal.calcd for C ₈₄H ₆₀N ₂(％):C,91.94；H,5.51；N,2.55；found:C,91.86；H,5.57；N,2.57。 In a 250mL Schlenk bottle, add 2.00g (4.74mmol) of Intermediate 83A, 1.00g (2.06mmol) of 1,6-diisopropyl-3,8-dibromopyrene, and tris(dibenzylideneacetone)dipalladium 0.09g (0.1mmol), 0.06g (0.2mmol) of tri-tert-butylphosphine tetrafluoroborate, 0.99g (10.31mmol) of sodium tert-butoxide, 100mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 1.55 g of white crystals are obtained, and the yield is 66.76%. MS(EI): m/z 1096.75[M+]. Anal.calcd for C ₈₄ H ₆₀ N ₂ (%): C, 91.94; H, 5.51; N, 2.55; found: C, 91.86; H, 5.57; N ,2.57.

制备例4：Preparation Example 4:

本制备例用于制备化合物87，其结构式及合成路线如下图所示：This preparation example is used to prepare compound 87, and its structural formula and synthetic route are shown in the following figure:

中间体87A的合成Synthesis of intermediate 87A

在250mL Schlenk瓶中，加入3-溴-9,9'-螺双芴4.68g(11.83mmol)，4-异丙基苯胺2.00g(14.79mmol)，醋酸钯0.17g(0.74mmol)，三叔丁基膦四氟硼酸盐0.43g(1.48mmol)，叔丁醇钠4.26g(44.38mmol)，甲苯120mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用100mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝2:1(V/V))，蒸去溶剂，干燥后，得到5.65g白色结晶，收率为85％。MS(EI):m/z 449.71[M+].Anal.calcd for C ₃₄H ₂₇N(％):C,90.83；H,6.05；N,3.12；found:C,90.73；H,6.13；N,3.14。 In a 250mL Schlenk bottle, add 4.68g (11.83mmol) of 3-bromo-9,9'-spirobisfluorene, 2.00g (14.79mmol) of 4-isopropylaniline, 0.17g (0.74mmol) of palladium acetate, and tertiary 0.43 g (1.48 mmol) of butyl phosphine tetrafluoroborate, 4.26 g (44.38 mmol) of sodium tert-butoxide, 120 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 100 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 2:1 (V/V)), the solvent is evaporated, and after drying, 5.65 g of white crystals are obtained with a yield of 85%. MS(EI): m/z 449.71[M+].Anal.calcd for C ₃₄ H ₂₇ N(%): C,90.83; H,6.05; N,3.12; found: C,90.73; H,6.13; N, 3.14.

化合物87的合成Synthesis of compound 87

在250mL Schlenk瓶中，加入中间体87A 5.00g(11.12mmol)，1,6-二异丙基-3,8-二溴芘1.98g(4.45mmol)，三(二亚苄基丙酮)二钯0.20g(0.22mmol)，三叔丁基膦四氟硼酸盐0.13g(0.44mmol)，叔丁醇钠2.14g(22.24mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用150mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝3:1(V/V))，蒸去溶剂，干燥后，得到3.30g白色结晶，收率为62.8％。MS(EI):m/z 1180.54[M+].Anal.calcd for C ₉₀H ₇₂N ₂(％):C,91.49；H,6.14；N,2.37；found:C,91.34；H,6.37；N,2.29。 In a 250mL Schlenk bottle, add intermediate 87A 5.00g (11.12mmol), 1,6-diisopropyl-3,8-dibromopyrene 1.98g (4.45mmol), tris(dibenzylideneacetone)dipalladium 0.20g (0.22mmol), 0.13g (0.44mmol) of tri-tert-butylphosphine tetrafluoroborate, 2.14g (22.24mmol) of sodium tert-butoxide, 150mL of toluene, under the protection of argon, reflux and stir for 12 hours. The reaction is complete. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.30 g of white crystals are obtained, with a yield of 62.8%. MS(EI): m/z 1180.54[M+]. Anal.calcd for C ₉₀ H ₇₂ N ₂ (%): C, 91.49; H, 6.14; N, 2.37; found: C, 91.34; H, 6.37; N , 2.29.

制备例5：Preparation Example 5:

本制备例用于制备化合物98，其结构式及合成路线如下图所示：This preparation example is used to prepare compound 98, and its structural formula and synthetic route are shown in the figure below:

化合物98的合成Synthesis of compound 98

在250mL Schlenk瓶中，加入中间体74A 6.00g(21.02mmol)，6,12-二溴屈3.25g(8.41mmol)，三(二亚苄基丙酮)二钯0.38g(0.42mmol)，三叔丁基膦四氟硼酸盐0.24g(0.84mmol)，叔丁醇钠4.04g(42.05mmol)，甲苯150mL，在氩气保护下，回流搅拌反应12小时，反应完毕。蒸去溶剂，用150mL二氯甲烷和50mL水溶解残留物，水洗，分出有机层，水层用15mL二氯甲烷萃取两次，合并有机层，蒸去溶剂后，残留物经柱层析分离(硅胶为350目，淋洗液为石油醚:二氯甲烷＝3:1(V/V))，蒸去溶剂，干燥后，得到3.60g白色结晶，收率为60.2％。MS(EI):m/z 794.87[M+].Anal.calcd for C ₆₀H ₄₆N ₂(％):C,90.64；H,5.83；N,3.52；found:C,90.62；H,6.87；N,2.51。 In a 250mL Schlenk bottle, add 6.00g (21.02mmol) of intermediate 74A, 3.25g (8.41mmol) of 6,12-dibromide, 0.38g (0.42mmol) of tris(dibenzylideneacetone) dipalladium, and tert 0.24 g (0.84 mmol) of butyl phosphine tetrafluoroborate, 4.04 g (42.05 mmol) of sodium tert-butoxide, 150 mL of toluene, under the protection of argon, the reaction was refluxed and stirred for 12 hours, and the reaction was completed. Evaporate the solvent, dissolve the residue with 150 mL of dichloromethane and 50 mL of water, wash with water, separate the organic layer, extract the aqueous layer twice with 15 mL of dichloromethane, combine the organic layers, evaporate the solvent, and separate the residue by column chromatography (The silica gel is 350 mesh, the eluent is petroleum ether: dichloromethane = 3:1 (V/V)), the solvent is evaporated, and after drying, 3.60 g of white crystals are obtained, with a yield of 60.2%. MS(EI): m/z 794.87[M+]. Anal.calcd for C ₆₀ H ₄₆ N ₂ (%): C,90.64; H,5.83; N,3.52; found: C,90.62; H,6.87; N ,2.51.

下面是本公开化合物的应用实施例The following are application examples of the compounds of the present disclosure

实施例Example

将空穴注入层3、空穴传输层I 4、空穴传输层II 5、电子阻挡层6、发光层7、空穴阻挡层8、电子传输层9、电子注入层10和阴极11依次形成在预先形成为玻璃基板1上的透明阳极2上，以制备如图3所示的有机电致发光器件。The hole injection layer 3, the hole transport layer I 4, the hole transport layer II 5, the electron blocking layer 6, the light emitting layer 7, the hole blocking layer 8, the electron transport layer 9, the electron injection layer 10, and the cathode 11 are sequentially formed On the transparent anode 2 previously formed on the glass substrate 1 to prepare an organic electroluminescent device as shown in FIG. 3.

具体地，将涂布了厚度为100nm的ITO透明导电层的玻璃基板在Decon 90碱性清洗液中超声处理，去离子水中冲洗，在丙酮和乙醇中各清洗三次，在洁净的环境下烘烤至完全除去水分，用紫外光和臭氧清洗，并用低能阳离子束轰击表面。将该带有ITO电极的玻璃基板置入真空腔内，抽真空至4×10 ^-5～2×10 ^-5Pa。 Specifically, the glass substrate coated with a transparent conductive layer of ITO with a thickness of 100nm was ultrasonically processed in Decon 90 alkaline cleaning solution, rinsed in deionized water, rinsed in acetone and ethanol three times each, and baked in a clean environment To completely remove the water, clean with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam. The glass substrate with the ITO electrode is placed in the vacuum chamber and evacuated to 4×10 ^-5 to 2×10 ^-5 Pa.

然后在上述带有ITO电极的玻璃基板上以0.2nm/s的蒸镀速率蒸镀2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HAT-CN)以形成膜厚为10nm的层作为空穴注入层(HIL)，在空穴注入层上，以2.0nm/s的蒸镀速率蒸镀N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)以形成膜厚为40nm的层作为空穴传输层I(HTL I)，然后在空穴传输层I(HTL I)上，以2.0nm/s的蒸镀速率蒸镀9,9',9”-三苯基-9H,9'H,9”H-3,3':6',3”-三咔唑(Tris-PCz)以形成膜厚为20nm的层作为空穴传输层II(HTL II)。在空穴传输层II上，以2.0nm/s的蒸镀速率蒸镀3,3'-二(N-咔唑基)-1,1'-联苯(mCBP)以形成膜厚为15nm的层作为电子阻挡层(EBL)，在电子阻挡层上，以9-(4-(1-萘基)-10-(2-萘基)蒽(NNPA)的蒸镀速率为2.0nm/s与制备例1、2、3、4、5的化合物(化合物44、74、83、87和98)的蒸镀速率为0.16nm/s的蒸镀速率进行双源共蒸，形成膜厚为20nm的层作为发光层，制备例1、2、3、4和5的化合物(化合物44、74、83、87和98)的掺杂质量比例为8wt％。在发光层上，以2.0nm/s的蒸镀速率蒸镀2,4,6-三(3-苯基)-1,3,5-三嗪(T2T)以形成膜厚为10nm的层作为空穴阻挡层(HBL)。在空穴阻挡层上，以2.0nm/s的蒸镀速率蒸镀2-[4-(9,10-二萘-2-蒽-2-基)苯基]-1-苯基-1H-苯并咪唑(ZADN)以形成膜厚为40nm的层作为电子传输层(ETL)。在电子传输层上，以0.2nm/s的蒸镀速率蒸镀8-羟基喹啉-锂(Liq)以形成膜厚为2nm的层作为电子注入层。最后，以3.0nm/s以上的蒸镀速率蒸镀铝，形成膜厚为100nm的阴极。Then, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexacyano-1,4,5,8,9,12- is evaporated on the above-mentioned glass substrate with ITO electrode at an evaporation rate of 0.2nm/s Hexaazatriphenylene (HAT-CN) is formed with a thickness of 10nm as the hole injection layer (HIL). On the hole injection layer, N, N'is deposited at an evaporation rate of 2.0nm/s -Diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) to form a layer with a thickness of 40nm as the hole transport layer I ( HTL I), and then on the hole transport layer I (HTL I), 9,9',9”-triphenyl-9H,9'H,9”H- is evaporated at an evaporation rate of 2.0nm/s 3,3':6',3”-tricarbazole (Tris-PCz) is formed with a thickness of 20nm as the hole transport layer II (HTL II). On the hole transport layer II, the thickness is 2.0nm/ s evaporation rate 3,3'-bis(N-carbazolyl)-1,1'-biphenyl (mCBP) is evaporated to form a layer with a film thickness of 15nm as the electron blocking layer (EBL). On the layer, the evaporation rate of 9-(4-(1-naphthyl)-10-(2-naphthyl)anthracene (NNPA) is 2.0nm/s and that of Preparation Examples 1, 2, 3, 4, 5 The vapor deposition rate of the compounds (compounds 44, 74, 83, 87, and 98) was 0.16nm/s. The vapor deposition rate was 0.16nm/s. Dual source co-evaporation was performed to form a layer with a thickness of 20nm as the light-emitting layer. Preparation Examples 1, 2, 3 The doping mass ratio of the compounds of, 4, and 5 (compounds 44, 74, 83, 87, and 98) is 8wt%. On the light-emitting layer, 2,4,6-three are evaporated at an evaporation rate of 2.0nm/s. (3-Phenyl)-1,3,5-triazine (T2T) is formed with a thickness of 10nm as the hole blocking layer (HBL). On the hole blocking layer, vapor deposition is performed at 2.0nm/s Rate deposition of 2-[4-(9,10-dinaphthalene-2-anthracene-2-yl)phenyl]-1-phenyl-1H-benzimidazole (ZADN) to form a layer with a thickness of 40nm as Electron transport layer (ETL). On the electron transport layer, 8-hydroxyquinoline-lithium (Liq) is vapor-deposited at a vapor deposition rate of 0.2 nm/s to form a layer with a thickness of 2 nm as the electron injection layer. Finally, use Aluminum is vapor deposited at a vapor deposition rate of 3.0 nm/s or more to form a cathode with a film thickness of 100 nm.

器件性能测试：器件的电流-亮度-电压特性是由带有校正过的硅光电二极管的Keithley源测量系(Keithley 2400 Sourcemeter、Keithley 2000 Currentmeter)完成的，电致发光光谱是由Photo research公司PR655光谱仪测量的，器件的外部量子效率通过文献Adv.Mater.,2003,15,1043–1048的方法计算可得。器件寿命是指以10000坎特拉每平方米为起始亮度，衰减到9000坎特拉每平方米(90％)的时间。所有器件均在氮气环境中封装。Device performance test: The current-brightness-voltage characteristics of the device are completed by the Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode, and the electroluminescence spectrum is performed by the Photoresearch company PR655 spectrometer Measured, the external quantum efficiency of the device can be calculated by the method of Adv. Mater., 2003, 15, 1043-1048. The lifetime of the device refers to the time for the brightness to decay to 9,000 canter per square meter (90%) starting with 10,000 canter per square meter. All devices are packaged in a nitrogen environment.

实施例涉及的化合物结构如下：The structures of the compounds involved in the examples are as follows:

实施例制备的有机电致发光器件(OLED1-5)的结构和各层的膜厚厚度如下：The structure of the organic electroluminescent device (OLED1-5) prepared in the example and the film thickness of each layer are as follows:

OLED1：OLED1:

ITO/HAT-CN(10nm)/NPB(40nm)/ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:44(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)mCBP(15nm)/NNPA:44(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED2：OLED2:

ITO/HAT-CN(10nm)/NPB(40nm)/ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:74(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)mCBP(15nm)/NNPA:74(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED3：OLED3:

ITO/HAT-CN(10nm)/NPB(40nm)/ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:83(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)mCBP(15nm)/NNPA:83(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED4：OLED4:

ITO/HAT-CN(10nm)/NPB(40nm)/ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:87(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)mCBP(15nm)/NNPA:87(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

OLED5：OLED5:

ITO/HAT-CN(10nm)/NPB(40nm)/ITO/HAT-CN(10nm)/NPB(40nm)/

mCBP(15nm)/NNPA:98(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)mCBP(15nm)/NNPA:98(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

比较例Comparative example

比较例1和2的制备方法与实施例相同，仅是改变荧光发光化合物。The preparation methods of Comparative Examples 1 and 2 are the same as the Examples, except that the fluorescent light-emitting compound is changed.

比较例1的器件结构如下：The device structure of Comparative Example 1 is as follows:

ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:DPAVBi(20nm,8wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:DPAVBi(20nm, 8wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

比较例2的器件结构如下：The device structure of Comparative Example 2 is as follows:

ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:C545T(20nm,5wt％)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)ITO/HAT-CN(10nm)/NPB(40nm)/mCBP(15nm)/NNPA:C545T(20nm, 5wt%)/T2T(10nm)/ZADN(40nm)/Liq(2nm)/Al(100nm)

实施例和比较例的器件的性能数据见下表1。The performance data of the devices of the embodiment and the comparative example are shown in Table 1 below.

表1器件性能数据Table 1 Device performance data

由表1可见，与比较例1和2相比，用本公开荧光发光材料制备的绿色和蓝色有机电致发光器件的发光效率和器件寿命明显提高。另外，蓝色有机电致发光器件的色纯度明显好于采用现有技术中的天蓝色材料DPAVBi所制备的有机电致发光器件。It can be seen from Table 1 that compared with Comparative Examples 1 and 2, the luminous efficiency and device lifetime of the green and blue organic electroluminescent devices prepared with the fluorescent light-emitting materials of the present disclosure are significantly improved. In addition, the color purity of the blue organic electroluminescent device is obviously better than that of the organic electroluminescent device prepared by using the sky blue material DPAVBi in the prior art.

产业上的可利用性Industrial availability

本公开的有机电致发光化合物具有极好的发光效率，优异的材料色纯度和寿命特性。因此，由该化合物可以制备具有极佳使用寿命的有机电致发光器件。The organic electroluminescent compound of the present disclosure has excellent luminous efficiency, excellent material color purity and lifetime characteristics. Therefore, organic electroluminescent devices with excellent service life can be prepared from the compound.

Claims

一种有机电致发光化合物，其由下述式(1)表示：An organic electroluminescent compound represented by the following formula (1):

在所述式(1)中，In the formula (1),

M表示C(R ¹) ₂或者 M means C(R ¹ ) ₂ or

其中虚线表示来自M的键；The dotted line represents the bond from M;

Z在每次出现时相同或不同，其表示C、CR ¹或者N； Z is the same or different every time it appears, which means C, CR ¹ or N;

A表示具有2至5个环的取代或者未取代的稠合芳环单元，Ar ¹、Ar ²在每次出现时相同或者不同地是具有5至30个芳族环原子并且可以被一个或者多个R ¹取代的芳族或杂芳族环系； A represents a substituted or unsubstituted condensed aromatic ring unit having 2 to 5 rings. Ar ¹ and Ar ² are the same or different each time they have 5 to 30 aromatic ring atoms and may be substituted by one or more A R ¹ substituted aromatic or heteroaromatic ring system;

R ¹在每次出现时相同或不同地是H、D、F、Cl、Br、I、CN、NO ₂、NR ²、OR ²、SR ²、C(＝O)R ²、P(＝O)R ²、Si(R ²) ₃、具有1至20个碳原子的取代或未取代的直链状或支链状的烷基、具有3至20个碳原子的取代或未取代的环状的烷基、具有2至20个碳原子的烯基或者炔基，或者具有5至40个芳族环原子并且在每种情况下可被一个或多个R ²取代的芳族或杂芳族环系；其中所述烷基、烯基或者炔基在每种情况下可被一个或者多个R ²取代，并且其中一个或者多个非相邻的CH ₂基团可被R ²C＝CR ²、C≡C、Si(R ²) ₃、C＝O、C＝NR ²、P(＝O)R ²、SO、SO ₂、NR ²、O、S或CONR ²代替，并且其中一个或者多个氢原子可以被D、F、Cl、Br、I、CN或NO ₂代替； R ¹ is the same or different each time H, D, F, Cl, Br, I, CN, NO ₂ , NR ² , OR ² , SR ² , C(=O)R ² , P(=O ) R ² , Si(R ² ) ₃ , substituted or unsubstituted linear or branched alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cyclic with 3 to 20 carbon atoms Alkyl, alkenyl or alkynyl having 2 to 20 carbon atoms, or aromatic or heteroaromatic having 5 to 40 aromatic ring atoms and in each case may be substituted by one or more R ² Ring system; wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more R ² in each case, and wherein one or more non-adjacent CH ₂ groups may be R ² C=CR ^2. C≡C, Si(R ² ) ₃ , C=O, C=NR ² , P(=O)R ² , SO, SO ₂ , NR ² , O, S or CONR ² instead, and one of them or Multiple hydrogen atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ;

其中，两个相邻的R ¹或两个相邻的R ²任选地形成单环或多环的脂族、芳族或者杂芳族的环系，所述环系可被一个或者多个R ²取代；并且两个或更多个R ¹可以彼此连接并形成环； Wherein, two adjacent R ¹ or two adjacent R ² optionally form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system, and the ring system may be composed of one or more R ^{2 is} substituted; and two or more R ¹ may be connected to each other and form a ring;

R ²在每种情况下相同或不同并且选自H、D、F、CN、具有1至20个碳原子的脂肪族基团、具有5至30个芳族环原子的芳族或杂芳族环系，或具有多环的脂肪族环系，其中一个或多个氢原子可以被D、F、CN取代。 R ² is the same or different in each case and is selected from H, D, F, CN, aliphatic groups having 1 to 20 carbon atoms, aromatic or heteroaromatic groups having 5 to 30 aromatic ring atoms A ring system, or an aliphatic ring system with multiple rings, in which one or more hydrogen atoms can be substituted by D, F, or CN.
根据权利要求1所述的有机电致发光化合物，其中所述式(1)中的A具有选自下列式所组成的群组中的一种结构：The organic electroluminescent compound according to claim 1, wherein A in the formula (1) has a structure selected from the group consisting of the following formulas:

其中R ₂至R ₁₅独立地选自由氢原子、具有1至20个碳原子的取代或未取代的烷基、具有6至30个碳原子的取代或未取代的芳基，以及具有3至30个碳原子的取代或未取代的杂芳族基所组成的群组。 Wherein R ₂ to R _{15 are} independently selected from hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, and groups having 3 to 30 carbon atoms. A group of substituted or unsubstituted heteroaromatic groups with three carbon atoms.
根据权利要求1或2所述的有机电致发光化合物，其由下述式(1-1)～式(1-4)中的任一个表示：The organic electroluminescent compound according to claim 1 or 2, which is represented by any one of the following formulas (1-1) to (1-4):

其中，Ar ¹、Ar ²、M、Z以及A与式(1)中定义相同。 Among them, Ar ¹ , Ar ² , M, Z, and A are the same as defined in formula (1).
根据权利要求1～3中任一项所述的有机电致发光化合物，其中，由所述式(1)表示的化合物选自下述化合物：The organic electroluminescent compound according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is selected from the following compounds:
一种发光材料，其包含根据权利要求1～4中任一项所述的有机电致发光化合物。A luminescent material comprising the organic electroluminescent compound according to any one of claims 1 to 4.
根据权利要求5所述的发光材料，其为荧光发光客体材料。The luminescent material of claim 5, which is a fluorescent luminescent guest material.
一种有机电致发光器件，其包括：第一电极、与所述第一电极对置而具备的第二电极、以及夹在所述第一电极与所述第二电极之间的至少一个有机层，An organic electroluminescence device comprising: a first electrode, a second electrode provided opposite to the first electrode, and at least one organic electroluminescence device sandwiched between the first electrode and the second electrode. layer,

其中所述有机层包含根据权利要求1～4中任一项所述的有机电致发光化合物。Wherein the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 4.
根据权利要求7所述的有机电致发光器件，其中，包含所述有机电致发光化合物的有机层为发光层。The organic electroluminescent device according to claim 7, wherein the organic layer containing the organic electroluminescent compound is a light emitting layer.