用于有机电致发光器件的有机化合物及有机电致发光器件Organic compounds for organic electroluminescent devices and organic electroluminescent devices
技术领域technical field
本发明涉及有机发光材料技术领域,具体涉及一种有机化合物、其应用以及包含其的有机电致发光器件。The present invention relates to the technical field of organic light-emitting materials, in particular to an organic compound, its application and an organic electroluminescent device comprising the same.
背景技术Background technique
近年来,基于有机材料的光电子器件已经变得越来越受欢迎。有机材料固有的柔性令其十分适合用于在柔性基板上制造,可根据需求设计、生产出美观而炫酷的光电子产品,获得相对于无机材料无以比拟的优势。此类有机光电子器件的示例包括有机发光二极管(OLED)、有机场效应管、有机光伏打电池及有机传感器等。其中OLED发展尤其迅速,已经在信息显示领域取得商业上的成功。OLED可以提供高饱和度的红、绿、蓝三颜色,用其制成的全色显示装置无需额外的背光源,具有色彩炫丽,轻薄柔软等优点。In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them very suitable for manufacturing on flexible substrates. It can design and produce beautiful and cool optoelectronic products according to requirements, and obtain incomparable advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light emitting diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLED has developed rapidly and has achieved commercial success in the field of information display. OLED can provide three colors of red, green and blue with high saturation. The full-color display device made of OLED does not need additional backlight, and has the advantages of dazzling colors, lightness and softness.
OLED器件核心为含有多种有机功能材料的薄膜结构。常见的功能化有机材料有:空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料、电子阻挡材料以及发光主体材料和发光客体(染料)等。通电时,电子和空穴被分别注入、传输到发光区域并在此复合,从而产生激子并发光。The core of an OLED device is a thin film structure containing a variety of organic functional materials. Common functionalized organic materials include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, light-emitting host materials and light-emitting guests (dyes), etc. When energized, electrons and holes are injected into and transported to the light-emitting region and recombined there, thereby generating excitons and emitting light.
人们已经开发出多种有机材料,结合各种奇特的器件结构,可以提升载流子迁移率、调控载流子平衡、突破电致发光效率、延缓器件衰减。出于量子力学的原因,常见的荧光发光体主要利用电子和空血结合时产生的单线态激子发光,现在仍然广泛地应用于各种OLED产品中。有些金属络合物如铱络合物,可以同时利用三线态激子和单线态激子进行发光,被称为磷光发光体,其能量转换效率可以比传统的荧光发光体提升高达四倍。热激发延迟荧光(TADF)技术通过促进三线态激子朝单线态激子的转变,在不采用金属配合物的情况下,仍然可以有效地利用三线态激子而实现较高的发光效率。热激发敏化荧光(TASF)技术则采用具TADF性质的材料,通过能量转移的方式来敏化发光体,同样可以实现较高的发光效率。A variety of organic materials have been developed, combined with various peculiar device structures, which can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device decay. For quantum mechanical reasons, common fluorescent emitters mainly utilize singlet excitons generated when electrons combine with empty blood to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously use triplet excitons and singlet excitons to emit light, which are called phosphorescent emitters, and their energy conversion efficiency can be up to four times higher than that of traditional fluorescent emitters. Thermally excited delayed fluorescence (TADF) technology can effectively utilize triplet excitons to achieve high luminous efficiency without using metal complexes by promoting the transition of triplet excitons to singlet excitons. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize the luminophore through energy transfer, which can also achieve high luminous efficiency.
近来,有文献报道了一种基于B-N共振结构的TADF(Thermally Activated Delayed Fluorescence,热活化延迟荧光)的超纯蓝色荧光化合物C1和C2,该类化合物由B、N以及苯环构成了刚性多环的芳香族骨架。氮原子具有与硼原子相反的共振效应,且在其对位的位置上相反的共振效应会增强。因此,这种效应可以很明显的分离HOMO和LUMO轨道,因而具有一定的TADF特性。Recently, a kind of ultrapure blue fluorescent compounds C1 and C2 based on TADF (Thermally Activated Delayed Fluorescence, Thermally Activated Delayed Fluorescence) based on the BN resonance structure have been reported in the literature. The aromatic skeleton of the ring. Nitrogen atoms have an opposite resonance effect to that of boron atoms, and the opposite resonance effect is enhanced at its para position. Therefore, this effect can clearly separate the HOMO and LUMO orbitals, and thus has certain TADF properties.
发明内容SUMMARY OF THE INVENTION
发明要解决的问题Invention to solve problem
随着OLED产品逐步进入市场,人们对上述这类产品的性能有越来越高的要求。当前使用的OLED材料和器件结构无法完全解决OLED产品效率、寿命、成本等各方面的问题。在深蓝光器件方面,该问题尤为突出。As OLED products gradually enter the market, people have higher and higher requirements for the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, lifespan, cost and other aspects. This problem is particularly prominent in deep blue light devices.
鉴于上述现有技术的问题,本发明的目的在于提供一类用于有机电致发光器件的新的化合物,使用这类化合物的有机电致发光器件能够发出深蓝光,其能够满足对OLED器件的光电性能和使用寿命不断提升的需求。本申请中,如果没有特别说明,“深蓝光”是指波长约440nm~470nm的光。In view of the above-mentioned problems in the prior art, the object of the present invention is to provide a new class of compounds for organic electroluminescent devices. The organic electroluminescent devices using such compounds can emit deep blue light, which can satisfy the requirements for OLED devices. The demand for ever-increasing optoelectronic performance and service life. In this application, unless otherwise specified, "deep blue light" refers to light with a wavelength of about 440 nm to 470 nm.
解决问题的方案solution to the problem
本发明的研究人员通过认真思考和不断实验,提出了一种巧妙的分子设计方案。令人惊讶地,经由上述方案得到的化合物非常适合应用于OLED中,所得的器件的性能优异,能够满足人们的要求。The researchers of the present invention have come up with an ingenious molecular design scheme through serious thinking and continuous experiments. Surprisingly, the compound obtained through the above scheme is very suitable for application in OLED, and the obtained device has excellent performance and can meet people's requirements.
具体而言,本发明的目的之一是提供一种有机化合物,具有如式(1)所示的结构:Specifically, one of the objects of the present invention is to provide an organic compound having the structure shown in formula (1):
其中,in,
X
1和X
2各自独立地选自CR
1R
2、NR
3、O、S或SiR
4R
5中的一种;
X 1 and X 2 are each independently selected from one of CR 1 R 2 , NR 3 , O, S or SiR 4 R 5 ;
当R
1~R
5中的任意一个或几个存在时,其任选与环A或环D成环;
When any one or more of R 1 to R 5 exists, it can optionally form a ring with Ring A or Ring D;
环A、环D和环E各自独立地选自取代或未取代的C5~C30芳环、取代或未取代的C3~C30芳杂环中的一种,且至少一个具有式(a)所示的结构,(a)所示的结构通过环F稠合(以形成式(1) 结构的化合物,即当环A、环D和环E中的任意一个或多个具有式(a)所示的结构时,其各自独立地通过式(a)上的环F与母核结构稠合,从而形成具有式(1)结构的化合物);Ring A, Ring D and Ring E are each independently selected from one of substituted or unsubstituted C5-C30 aromatic rings and substituted or unsubstituted C3-C30 aromatic heterocycles, and at least one has the formula (a) The structure shown in (a) is fused through ring F (to form a compound of formula (1), that is, when any one or more of ring A, ring D and ring E has the formula (a) When the structure of , each independently is fused with the parent core structure through the ring F on the formula (a), thereby forming a compound with the structure of the formula (1));
环F和环G各自独立地选自取代或未取代的C5~C23芳环、取代或未取代的C3~C23芳杂环中的一种;Ring F and Ring G are each independently selected from substituted or unsubstituted C5-C23 aromatic rings and substituted or unsubstituted C3-C23 aromatic heterocycles;
Y
1和Y
2各自独立地选自CR
6R
7、NR
8、O、S或SiR
9R
10中的一种;
Y 1 and Y 2 are each independently selected from one of CR 6 R 7 , NR 8 , O, S or SiR 9 R 10 ;
R
1~R
10独立地选自氢、卤素、氰基、硝基、羟基、取代或未取代的C1~C10链状烷基、取代或未取代的C3~C10环烷基、取代或未取代的C1~C10烷氧基、氨基、取代或未取代的C1~C10硅烷基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
R 1 to R 10 are independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 cycloalkyl One of the C1-C10 alkoxy, amino, substituted or unsubstituted C1-C10 silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;
当上述基团存在取代基时,所述取代基选自卤素、氰基、硝基、羟基、C1~C10链状烷基、C3~C10环烷基、C1~C10烷氧基、C1~C10硫代烷氧基、C1~C10硅烷基、氨基、C6~C30芳基氨基、C3~C30杂芳基氨基、C6~C30芳基、C3~C30杂芳基中的一种或者至少两种的组合。When the above group has a substituent, the substituent is selected from halogen, cyano, nitro, hydroxyl, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 One or at least two of thioalkoxy, C1-C10 silyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl and C3-C30 heteroaryl combination.
本发明的上述化合物作为发光材料性能优异的具体原因尚不明确,推测如下:满足本发明限定的通式(1)结构的化合物具有适宜的刚性共轭结构作为母核,并通过亚甲基、亚胺基、O或S等将特定的芳香基团连接至母核的同时打断母核与该基团之间的共轭结构,因此能在OLED器件中表现出较高的外量子效率以及较低的起降电压。将特定母核与特定芳香基团通过上述特定方式连接得到的化合物作为发光层染料时,在改善器件的电压和效率的同时,能够避免光色红移并提高光色纯度。The specific reasons for the excellent performance of the above-mentioned compounds of the present invention as light-emitting materials are not yet clear, but it is presumed as follows: the compounds satisfying the structure of the general formula (1) defined in the present invention have a suitable rigid conjugated structure as the mother nucleus, and pass the methylene, The imine group, O or S, etc. connect a specific aromatic group to the parent nucleus while breaking the conjugated structure between the parent nucleus and the group, so it can show high external quantum efficiency in OLED devices and Lower take-off and drop voltage. When a compound obtained by linking a specific core and a specific aromatic group in the above specific manner is used as a light-emitting layer dye, the voltage and efficiency of the device can be improved, and the red shift of the light color can be avoided and the light color purity can be improved.
本发明中,所述的“取代或未取代”的基团,可以取代有一个取代基,也可以取代有多个取代基,当取代基为多个时,可以选自不同的取代基,本发明中涉及到相同的表达方式时,均具有同样的意义,且取代基的选择范围均如上所示不再一一赘述。In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the invention, they all have the same meaning, and the selection ranges of the substituents are all as shown above and will not be repeated one by one.
在本说明书中,Ca~Cb的表达方式代表该基团具有的碳原子数为a~b,除非特殊说明,一般而言该碳原子数不包括取代基的碳原子数。In this specification, the expressions of Ca-Cb represent that the number of carbon atoms of the group is a-b, unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituent.
在本说明书中,“—”划过的环结构的表达方式,表示连接位点于该环结构上任意能够成键的位置。In the present specification, the expression of the ring structure crossed by "—" means that the connection site is at any position on the ring structure that can form a bond.
在本说明书中,“各自独立地”表示其主语具有多个时,彼此之间可以相同也可以不同。In this specification, "each independently" means that when the subject has a plurality of them, they may be the same or different from each other.
本发明中,对于化学元素的表述,若无特别说明,通常包含化学性质相同的同位素的概念,例如“氢(H)”的表述,也包括化学性质相同的
1H(氕或作H)、
2H(氘或作D)的概念;碳(C)则包括
12C、
13C等,不再赘述。
In the present invention, the expression of chemical elements, unless otherwise specified, usually includes the concept of isotopes with the same chemical properties, for example, the expression of "hydrogen (H)" also includes 1 H (protium or H), The concept of 2 H (deuterium or D); carbon (C) includes 12 C, 13 C, etc., and will not be repeated here.
本发明中的杂原子,通常指选自N、O、S、P、Si和Se中的原子或原子团,优选选自N、O、S。The heteroatoms in the present invention generally refer to atoms or atomic groups selected from N, O, S, P, Si and Se, preferably selected from N, O, S.
在本说明书中,作为卤素的例子可举出:氟、氯、溴、碘等。In this specification, fluorine, chlorine, bromine, iodine, etc. are mentioned as an example of a halogen.
本发明中,所述单环芳基是指分子中含有一个或至少两个苯基,当分子中含有至少两个苯基时,苯基之间相互独立,通过单键进行连接,示例性地如苯基、二联苯基、三联苯基等;稠环芳基是指分子中含有至少两个苯环,但苯环之间并不相互独立,而是共用环边彼此稠合起来,示例性地如萘基、蒽基等;单环杂芳基是指分子中含有至少一个杂芳基,当分子中含有一个杂芳基和其他基团(如芳基、杂芳基、烷基等)时,杂芳基和其他基团之间相互独立,通过单键进行连接,示例性地如吡啶、呋喃、噻吩等;稠环杂芳基是指由至少一个苯基和至少一个杂芳基稠合而成,或,由至少两种杂芳环稠合而成,示例性地如喹啉、异喹啉、苯并呋喃,二苯并呋喃,苯并噻吩,二苯并噻吩等。In the present invention, the monocyclic aryl group means that the molecule contains one or at least two phenyl groups. When the molecule contains at least two phenyl groups, the phenyl groups are independent from each other and are connected through a single bond, exemplarily Such as phenyl, biphenyl, terphenyl, etc.; fused-ring aryl refers to the molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but share ring edges and fused with each other, for example Such as naphthyl, anthracenyl, etc.; monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group, when the molecule contains a heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc. ), the heteroaryl group and other groups are independent of each other and are connected through a single bond, such as pyridine, furan, thiophene, etc.; Condensed, or, condensed from at least two heteroaromatic rings, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene and the like.
在本发明中,若无特别说明,芳基和杂芳基均包括单环和稠环的情况。In the present invention, unless otherwise specified, both the aryl group and the heteroaryl group include the case of a single ring and a condensed ring.
在本发明中,若无特别说明,则取代基与其所在的基团不发生稠合。In the present invention, unless otherwise specified, the substituent is not condensed with the group in which it is located.
本发明的有机化合物优选X
1和X
2各自独立地选自NR
3、O或S中的一种。本发明的有机化合物更优选X
1和X
2至少一个为NR
3,R
3为取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种。
The organic compound of the present invention is preferably X 1 and X 2 each independently selected from one of NR 3 , O or S. More preferably, in the organic compound of the present invention, at least one of X 1 and X 2 is NR 3 , and R 3 is one of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups.
通过将本发明的有机化合物设为上述结构,能够具有更高的载流子传输性能。By setting the organic compound of the present invention to have the above-mentioned structure, it is possible to have higher carrier transport performance.
本发明的有机化合物优选Y
1和Y
2各自独立地选自CR
6R
7、NR
8或O中的一种;更优选Y
1和Y
2至少一个为CR
6R
7;进一步优选Y
1和Y
2均为CR
6R
7。
In the organic compound of the present invention, preferably Y 1 and Y 2 are each independently selected from one of CR 6 R 7 , NR 8 or O; more preferably, at least one of Y 1 and Y 2 is CR 6 R 7 ; further preferably, Y 1 and Y 2 is both CR 6 R 7 .
本发明的有机化合物优选R
6和R
7各自独立地选自氢、取代或未取代的C1~C10链状烷基、取代或未取代的C3~C10环烷基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种;
In the organic compound of the present invention, preferably R 6 and R 7 are each independently selected from hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6- One of C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;
更优选R
6和R
7各自独立地选自氢或以下基团中的一种:
More preferably R 6 and R 7 are each independently selected from hydrogen or one of the following groups:
进一步优选R
6和R
7均为甲基。
It is further preferred that both R6 and R7 are methyl.
通过将本发明的有机化合物设为上述结构,能够避免光色红移并提高光色纯度。By making the organic compound of the present invention the above-mentioned structure, it is possible to avoid the red shift of the light color and to improve the light color purity.
本发明的有机化合物优选环F选自取代或未取代的C5~C14芳环、取代或未取代的C3~C14芳杂环中的一种;更优选选自取代或未取代的C5~C10芳环、取代或未取代的C3~C10含N芳杂环中的一种;进一步优选为式(b)所示的结构:The organic compound of the present invention is preferably one of ring F selected from substituted or unsubstituted C5-C14 aromatic rings and substituted or unsubstituted C3-C14 aromatic heterocycles; more preferably selected from substituted or unsubstituted C5-C10 aromatic rings One of ring, substituted or unsubstituted C3-C10 N-containing aromatic heterocycles; more preferably the structure represented by formula (b):
其中,*代表与Y
1Y
2环所在的环稠合的位点,环F通过Z
1和Z
2、Z
2和Z
3或者Z
3和Z
4与母核稠合,Z
1~Z
4各自独立地选自C、CR
11、N中的一种;所述R
11各自独立地选自氢、卤素、氰基、硝基、羟基、取代或未取代的C1~C10链状烷基、取代或未取代的C3~C10环烷基、取代或未取代的C1~C10烷氧基、取代或未取代的C1~C10硅烷基、氨基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种,所述R
11任选与相邻的芳环或芳杂环连接成环;
Wherein, * represents the condensed site with the ring in which the Y 1 Y 2 ring is located, and the ring F is condensed with the parent nucleus through Z 1 and Z 2 , Z 2 and Z 3 or Z 3 and Z 4 , and Z 1 to Z 4 Each is independently selected from one of C, CR 11 , and N; the R 11 is each independently selected from hydrogen, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C10 chain alkyl, Substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted Or one of unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and the R 11 is optionally connected to adjacent aryl groups. Rings or aromatic heterocycles are connected to form a ring;
更进一步优选Z
1~Z
4各自独立地为CR
11,所述R
11各自独立地选自氢或以下基团中的一种:
Still more preferably, each of Z 1 to Z 4 is independently CR 11 , and each of said R 11 is independently selected from hydrogen or one of the following groups:
通过将本发明的有机化合物设为上述结构,能在OLED器件中表现出更高的外量子效率以及更低的电压。By setting the organic compound of the present invention into the above-mentioned structure, higher external quantum efficiency and lower voltage can be exhibited in the OLED device.
本发明的有机化合物优选环A、环D和环E各自独立地选自取代或未取代的C5~C14芳环、取代或未取代的C3~C14芳杂环中的一种,且至少一个具有式(a)所示的结构;In the organic compound of the present invention, it is preferable that ring A, ring D and ring E are each independently selected from one of substituted or unsubstituted C5-C14 aromatic rings and substituted or unsubstituted C3-C14 aromatic heterocycles, and at least one of them has The structure shown in formula (a);
更优选环A和环D各自独立地选自式(c)或式(a)所示的结构,环E为式(c’)或式(a)所示的结构,且环A、环D和环D中至少一个具有式(a)所示的结构:More preferably, ring A and ring D are each independently selected from the structure represented by formula (c) or formula (a), ring E is a structure represented by formula (c') or formula (a), and ring A, ring D and at least one of ring D has the structure shown in formula (a):
其中,*代表与母核相连的位点,Z
5~Z
8分别独立地选自C、CR
11、N中的一种;所述R
11各自独立地选自氢、卤素、氰基、硝基、羟基、取代或未取代的C1~C10链状烷基、取代或未取代的C3~C10环烷基、取代或未取代的C1~C10烷氧基、取代或未取代的C1~C10硅烷基、氨基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种,R
11任选与相邻的芳环或芳杂环连接成环;
Wherein, * represents the site connected to the parent nucleus, Z 5 to Z 8 are each independently selected from one of C, CR 11 , and N; the R 11 is each independently selected from hydrogen, halogen, cyano, nitro group, hydroxyl, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 silane base, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl One of the bases, R 11 is optionally connected to the adjacent aromatic ring or aromatic heterocycle to form a ring;
进一步优选环A和环D中至少一个为式(a)所示的结构。More preferably, at least one of ring A and ring D is a structure represented by formula (a).
另外,优选Z
5~Z
8分别独立地为CR
11,R
11各自独立地选自氢或以下基团中的一种:
In addition, preferably Z 5 to Z 8 are each independently CR 11 , and R 11 is each independently selected from hydrogen or one of the following groups:
通过将本发明的有机化合物设为上述结构,能在OLED器件中表现出更高的外量子效率以及更低的电压。By setting the organic compound of the present invention into the above-mentioned structure, higher external quantum efficiency and lower voltage can be exhibited in the OLED device.
本发明的有机化合物优选环G选自取代或未取代的C5~C14芳环、取代或未取代的C3~C14芳杂环中的一种;In the organic compound of the present invention, preferably ring G is selected from one of substituted or unsubstituted C5-C14 aromatic rings and substituted or unsubstituted C3-C14 aromatic heterocycles;
更优选选自取代或未取代的C5~C10芳环,取代或未取代的C3~C10含N芳杂环中的一种;More preferably one selected from substituted or unsubstituted C5-C10 aromatic rings and substituted or unsubstituted C3-C10 N-containing aromatic heterocycles;
进一步优选为式(b’)所示的结构:Further preferred is the structure shown in formula (b'):
其中,*代表与Y
1Y
2环所在的环稠合的位点,Z
1’~Z
4’分别独立地选自C、CR
12、N中的一种;R
12独立地选自氢、卤素、氰基、硝基、羟基、取代或未取代的C1~C10链状烷基、取代或未取代的C3~C10环烷基、取代或未取代的C1~C10烷氧基、取代或未取代的C1~C10硅烷基、氨基、取代或未取代的C6~C30芳基氨基、取代或未取代的C3~C30杂芳基氨基、取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基中的一种,所述R
12任选与其所连接的芳环或芳杂环稠合成环。
Wherein, * represents the condensed site with the ring in which the Y 1 Y 2 ring is located, Z 1' to Z 4' are independently selected from one of C, CR 12 and N; R 12 is independently selected from hydrogen, Halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted Substituted C1-C10 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted One of the C3-C30 heteroaryl groups, the R 12 is optionally condensed with the aromatic ring or aromatic heterocyclic ring to which it is connected to form a ring.
通过将本发明的有机化合物设为上述结构,能在OLED器件中表现出更高的外量子效率以及更低的电压。By setting the organic compound of the present invention into the above-mentioned structure, higher external quantum efficiency and lower voltage can be exhibited in the OLED device.
本发明中提到的C1-C10的烷基可举出例如:甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正己基、正辛基、正壬基。The C1-C10 alkyl group mentioned in the present invention can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, Positive nonyl.
本发明中提到的C3~C10环烷基可举出例如:环丙基、环丁基、环戊基、环己基、环癸基等。The C3-C10 cycloalkyl group mentioned in the present invention includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group, and the like.
本发明中提到的C1-C10的烷氧基可举出例如:甲氧基、乙氧基、丁氧基、己氧基、辛氧基等。The C1-C10 alkoxy group mentioned in the present invention includes, for example, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, an octyloxy group, and the like.
本发明中提到的C1-C10的硫代烷氧基可举出例如:甲硫基、乙硫基、丁硫基、己硫基、辛硫基等。The C1-C10 thioalkoxy group mentioned in the present invention includes, for example, a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, an octylthio group, and the like.
本发明中提到的C1-C10的硅烷基可举出例如:三甲基硅烷基、三乙基硅烷基等。The C1-C10 silyl group mentioned in the present invention includes, for example, a trimethylsilyl group, a triethylsilyl group, and the like.
本发明中提到的C6~C30芳基氨基可举出例如:苯基氨基、甲基苯基氨基、萘基氨基、蒽基氨基、菲基氨基、联苯基氨基等。The C6-C30 arylamino group mentioned in the present invention includes, for example, phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrylamino, biphenylamino and the like.
本发明中提到的C3~C30杂芳基氨基可举出例如:吡啶基氨基、嘧啶基氨基、二苯并呋喃基氨基等。The C3-C30 heteroarylamino group mentioned in the present invention includes, for example, a pyridylamino group, a pyrimidinylamino group, a dibenzofuranylamino group, and the like.
本发明中提到的C6-C30的芳基包括C6-30的单环芳基和C10-C30的稠环芳基。C6-30的单环芳基可举出例如:苯基、联苯基、三联苯基等。具体而言,所述联苯基包括2-联苯基、3-联苯基和4-联苯基;所述三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基。C10~C30稠环芳基可举出例如:萘基、蒽基、菲基、茚基、芴基、荧蒽基、三亚苯基、芘基、苝基、
基、并四苯基及它们的衍生基团等。具体而言,所述萘基包括1-萘基或2-萘基;所述蒽基选自1-蒽基、2-蒽基和9-蒽基;所述芴基选自1-芴基、2-芴基、3-芴基、4-芴基和9-芴基;所述芘基选自1-芘基、2-芘基和4-芘基;所述并四苯基选自1-并四苯基、2-并四苯基和9-并四苯基。所述芴的衍生基团选自9,9-二甲基芴基、9,9-二乙基芴基、9,9-二丙基芴基、9,9-二丁基芴基、9,9-二戊基芴基、9,9-二己基芴基、9,9-二苯基芴基、9,9-二萘基芴基、螺芴基和苯并芴基。
The C6-C30 aryl group mentioned in the present invention includes a C6-30 monocyclic aryl group and a C10-C30 fused-ring aryl group. As a C6-30 monocyclic aryl group, a phenyl group, a biphenyl group, a terphenyl group, etc. are mentioned, for example. Specifically, the biphenyl group includes 2-biphenyl group, 3-biphenyl group and 4-biphenyl group; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl- 3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl. C10-C30 fused-ring aryl groups include, for example, naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, fluoranthyl, triphenylene, pyrenyl, perylene, group, naphthacyl group and their derivative groups, etc. Specifically, the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl , 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthacyl is selected from 1-naphthacyl, 2-naphthacyl and 9-naphthacyl. The derivative group of the fluorene is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dibutylfluorenyl ,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirofluorenyl and benzofluorenyl.
本发明中提到的C3~C30杂芳基包括C3~C30单环杂芳基和C6~C30稠环杂芳基。C3~C30单环杂芳基可举出例如:呋喃基、噻吩基、吡咯基、吡啶基等。C6~C30稠环杂芳基可举出例如:苯并呋喃基、苯并噻吩基、异苯并呋喃基、吲哚基、二苯并呋喃基、二苯并噻吩基、咔唑基、吖啶基、异苯并呋喃基、异苯并噻吩基、吖啶基、吡啶基、苯并咔唑基、氮杂咔唑基、吩噻嗪基、吩嗪基等。The C3-C30 heteroaryl groups mentioned in the present invention include C3-C30 monocyclic heteroaryl groups and C6-C30 fused-ring heteroaryl groups. For example, the C3-C30 monocyclic heteroaryl group includes a furyl group, a thienyl group, a pyrrolyl group, and a pyridyl group. Examples of C6-C30 fused ring heteroaryl groups include benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, acridine Peridyl, isobenzofuranyl, isobenzothienyl, acridinyl, pyridyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl and the like.
本发明中亚芳基的具体例,可以举出上述芳基的例子中去掉一个氢原子而得到的二价基团。本发明中亚杂芳基的具体例,可以举出上述杂芳基的例子中去掉一个氢原子而得到的二价基团。Specific examples of the arylene group in the present invention include divalent groups obtained by removing one hydrogen atom from the examples of the above-mentioned aryl group. Specific examples of the heteroarylene group in the present invention include divalent groups obtained by removing one hydrogen atom from the above examples of the heteroaryl group.
本发明中的芳氧基,可以举出上述芳基与杂芳基与氧组成的一价基团。The aryloxy group in the present invention includes a monovalent group consisting of the above-mentioned aryl group, heteroaryl group, and oxygen.
本发明中提到的C6~C30芳基氨基可举出例如:苯基氨基、甲基苯基氨基、萘基氨基、蒽基氨基、菲基氨基、联苯基氨基等。The C6-C30 arylamino group mentioned in the present invention includes, for example, phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrylamino, biphenylamino and the like.
本发明中提到的C3~C30杂芳基氨基可举出例如:吡啶基氨基、嘧啶基氨基、二苯并呋喃基氨基等。The C3-C30 heteroarylamino group mentioned in the present invention includes, for example, a pyridylamino group, a pyrimidinylamino group, a dibenzofuranylamino group, and the like.
以上分别对各基团的优选方案进行了说明,本领域技术人员可以在不违背本发明的主旨的前提下对其进行组合。以下给出通式(1)的部分子通式作为例子,但本发明的化合物结构不限于这些子通式。The preferred solutions of each group have been described above, and those skilled in the art can combine them without departing from the gist of the present invention. The partial sub-formulas of the general formula (1) are given below as examples, but the compound structures of the present invention are not limited to these sub-formulas.
进一步优选的,Further preferably,
进一步优选的,Further preferably,
以上各子通式中,Z
11~Z
18、Z
5’~Z
7’与前文中的Z
1~Z
4具有相同的范围,R
8’和R
8”与前文中的R
8具有相同的范围。
In the above sub-formulas, Z 11 to Z 18 , Z 5 ′ to Z 7 ′ have the same range as Z 1 to Z 4 in the foregoing, and R 8 ′ and R 8 ″ have the same range as R 8 in the foregoing. Scope.
更进一步的,本发明的通式化合物优选为下列具体的化合物,但本发明不限于下列所示的具体化合物:Further, the compound of the general formula of the present invention is preferably the following specific compounds, but the present invention is not limited to the following specific compounds:
作为本发明的另一个方面,还提供了一种如上所述的化合物在有机电致发光器件中的应用。具体说,优选为在有机电致发光器件中作为发光层材料。As another aspect of the present invention, there is also provided an application of the above compound in an organic electroluminescent device. Specifically, it is preferably used as a light-emitting layer material in an organic electroluminescent device.
作为本发明的又一个方面,还提供了一种有机电致发光器件,包括第一电极、第二电极和插入在所述第一电极和第二电极之间的有机层,该有机层中含有如上所述的通式(1)的化合物。As yet another aspect of the present invention, an organic electroluminescence device is also provided, comprising a first electrode, a second electrode and an organic layer interposed between the first electrode and the second electrode, the organic layer containing Compounds of general formula (1) as described above.
发明效果Invention effect
本发明通式(1)的化合物具有适宜的刚性共轭结构作为母核,并通过亚甲基、亚胺基、O或S等将特定的芳香基团连接至母核的同时打断母核与该基团之间的共轭结构,因此能在OLED器件中表现出较高的外量子效率以及较低的起降电压。将上述特定母核与上述特定芳香基团通过上述特定方式连接得到的化合物作为发光层染料时,在改善器件的电压和效率的同时,能够避免光色红移并提高光色纯度。经由上述方案得到的化合物非常适合应用于OLED中,所得的器件的性能优异,能够满足人们的要求。The compound of the general formula (1) of the present invention has a suitable rigid conjugated structure as a parent nucleus, and connects a specific aromatic group to the parent nucleus through a methylene group, an imino group, O or S, etc., while interrupting the parent nucleus The conjugated structure with this group can therefore show higher external quantum efficiency and lower take-off and fall voltage in OLED devices. When the compound obtained by linking the above specific core and the above specific aromatic group through the above specific method is used as a light emitting layer dye, the voltage and efficiency of the device can be improved, and the red shift of the light color can be avoided and the light color purity can be improved. The compound obtained through the above scheme is very suitable for application in OLED, and the obtained device has excellent performance and can meet people's requirements.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
合成例1:P1的合成Synthesis Example 1: Synthesis of P1
室温下,向500ml三口瓶中加入原料1(20g,88.54mmol),原料2(58g,177.07mmol),双 [二叔丁基-(4-二甲基氨基苯基)膦]二氯化钯(II)(2.5g,3.54mmol),叔丁醇钠(25.5g,265.61mmol),二甲苯(200ml)作溶剂,置换三次氮气,升温至120℃反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品55.0g(中间体M1)。At room temperature, in a 500ml there-necked flask, add raw material 1 (20g, 88.54mmol), raw material 2 (58g, 177.07mmol), bis[di-tert-butyl-(4-dimethylaminophenyl)phosphine]palladium dichloride (II) (2.5g, 3.54mmol), sodium tert-butoxide (25.5g, 265.61mmol), xylene (200ml) as solvent, nitrogen was replaced three times, the temperature was raised to 120°C and the reaction was stopped for 12h, then the heating was stopped, filtered and evaporated to dryness. Purification by chromatography (petroleum ether:dichloromethane=10:1) gave 55.0 g of product (intermediate M1).
将中间体M1(55g,72.04mmol)溶于500ml二甲苯中,在-40℃条件下缓慢滴加正丁基锂(86.4ml,216.12mmol),滴加完成后,恢复室温,在50℃条件下加热活化2h,后降温至-40℃,先后缓慢加入BBr3(45.03g,180.1mmol),和DIEA(37.2g,288.16mmol),恢复室温后加热110℃反应10h,后停止加热,水洗过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品19.8g(P1)。The intermediate M1 (55g, 72.04mmol) was dissolved in 500ml of xylene, and n-butyllithium (86.4ml, 216.12mmol) was slowly added dropwise at -40°C. It was heated and activated for 2h, then cooled to -40°C, slowly added BBr3 (45.03g, 180.1mmol), and DIEA (37.2g, 288.16mmol), returned to room temperature, heated at 110°C and reacted for 10h, then stopped heating, washed with water, filtered and evaporated. Dry, and purify by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 19.8 g of product (P1).
合成例(2):P16的合成Synthesis Example (2): Synthesis of P16
合成方法与合成例1类似,不同之处在于将原料2替换成等当量的原料3,得到产品56.6g(中间体M2)。P16的合成方法与P1类似,最终得到产品19.8g(P16)。The synthesis method is similar to that of Synthesis Example 1, except that the raw material 2 is replaced with an equivalent amount of the raw material 3 to obtain 56.6 g of the product (intermediate M2). The synthesis method of P16 was similar to that of P1, and the product 19.8g (P16) was finally obtained.
合成例(3):P29的合成Synthesis Example (3): Synthesis of P29
合成方法与合成例1类似,不同之处在于将原料1替换成等当量的原料4,得到产品28.2g(中间体M3)。P29的合成方法与P1类似,最终得到产品9.87g(P29)。The synthesis method was similar to that of Synthesis Example 1, except that the raw material 1 was replaced with an equivalent amount of the raw material 4 to obtain 28.2 g of the product (intermediate M3). The synthesis method of P29 was similar to that of P1, and the final product 9.87g (P29) was obtained.
合成例(4):P53的合成Synthesis Example (4): Synthesis of P53
室温下,向500ml三口瓶中加入原料1(10g,44.27mmol),原料2(14.45g,44.27mmol),(DBA)3Pd2(0.81g,0.88mmol),三叔丁基膦四氟硼酸盐(0.51g,1.77mmol),叔丁醇钠(10.62g,110.68mmol),甲苯(100ml)作溶剂,置换三次氮气,升温至回流反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品15g(中间体M4)。At room temperature, add raw material 1 (10g, 44.27mmol), raw material 2 (14.45g, 44.27mmol), (DBA) Pd (0.81g, 0.88mmol), tri-tert-butylphosphine tetrafluoroborate to a 500ml there-necked flask (0.51g, 1.77mmol), sodium tert-butoxide (10.62g, 110.68mmol), toluene (100ml) as solvent, nitrogen was replaced three times, heating was stopped after being heated to reflux for 12h, filtered and evaporated to dryness, purified by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 15 g of product (intermediate M4).
室温下,向500ml三口瓶中加入中间体M4(15g,31.75mmol),原料3(5.4g,31.75mmol),Pd132(0.45g,0.64mmol),叔丁醇钠(7.62g,79.4mmol),二甲苯(200ml)作溶剂,置换三次氮气,升温至120℃反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品16.7g(中间体M5)。At room temperature, in a 500ml there-necked flask, add intermediate M4 (15g, 31.75mmol), raw material 3 (5.4g, 31.75mmol), Pd132 (0.45g, 0.64mmol), sodium tert-butoxide (7.62g, 79.4mmol), Xylene (200ml) was used as the solvent, nitrogen was replaced three times, the temperature was raised to 120°C and the reaction was stopped for 12h, then the heating was stopped, filtered and evaporated to dryness, and purified by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 16.7g of the product (intermediate M5).
将中间体M5(16.7g,27.63mmol)溶于200ml二甲苯中,在-40℃条件下缓慢滴加正丁基锂(33.2ml,82.88mmol),滴加完成后,恢复室温,在50℃条件下加热活化2h,后降温至-40℃,先后缓慢加入BBr3(17.27g,69.1mmol),和DIEA(14.26g,110.52mmol),恢复室温后加热110℃反应10h,后停止加热,水洗过滤蒸干,柱层析提纯(石油醚:二氯甲烷=20:1),得到产品6.78g(P53)。The intermediate M5 (16.7 g, 27.63 mmol) was dissolved in 200 ml of xylene, and n-butyllithium (33.2 ml, 82.88 mmol) was slowly added dropwise at -40 °C. It was heated and activated for 2h under the conditions, and then cooled to -40°C. BBr3 (17.27g, 69.1mmol) and DIEA (14.26g, 110.52mmol) were slowly added successively. After returning to room temperature, the reaction was heated at 110°C for 10h, and then the heating was stopped, washed with water and filtered. Evaporate to dryness, and purify by column chromatography (petroleum ether:dichloromethane=20:1) to obtain 6.78g of product (P53).
合成例(5):材料54的合成Synthesis Example (5): Synthesis of Material 54
合成方法与合成例4类似,不同之处在于将原料5替换成等当量的原料6,得到产品11.3g(中间体M6)。P54的合成方法与P53类似,最终得到产品4.6g(P54)。The synthesis method was similar to that of Synthesis Example 4, except that the raw material 5 was replaced with an equivalent amount of the raw material 6 to obtain 11.3 g of the product (intermediate M6). The synthesis method of P54 was similar to that of P53, and finally 4.6 g of the product (P54) was obtained.
合成例(6):P84的合成Synthesis Example (6): Synthesis of P84
室温下,向500ml三口瓶中加入中间体M4(10g,21.17mmol),原料7(5.96g,21.17mmol),Pd132(0.3g,0.42mmol),叔丁醇钠(5.1g,52.93mmol),二甲苯(200ml)作溶剂,置换三次氮气,升温至120℃反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品10.8g(中间体M7)。At room temperature, in a 500ml there-necked flask, add intermediate M4 (10g, 21.17mmol), raw material 7 (5.96g, 21.17mmol), Pd132 (0.3g, 0.42mmol), sodium tert-butoxide (5.1g, 52.93mmol), Xylene (200ml) was used as the solvent, nitrogen was replaced three times, the temperature was raised to 120°C and the reaction was stopped for 12h, then the heating was stopped, filtered and evaporated to dryness, and purified by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 10.8g of the product (intermediate M7).
将中间体M7(10.8g,15.60mmol)溶于100ml二甲苯中,在-40℃条件下缓慢滴加正丁基锂(18.12ml,45.29mmol),滴加完成后,恢复室温,在50℃条件下加热活化2h,后降温至-40℃,先后缓慢加入BBr3(9.75g,39mmol),和DIEA(8.04g,62.4mmol),恢复室温后加热110℃反应10h,后停止加热,水洗过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品4.2g(P84)。The intermediate M7 (10.8 g, 15.60 mmol) was dissolved in 100 ml of xylene, and n-butyllithium (18.12 ml, 45.29 mmol) was slowly added dropwise at -40 °C. It was heated and activated under the conditions for 2h, then cooled to -40°C, slowly added BBr3 (9.75g, 39mmol), and DIEA (8.04g, 62.4mmol), returned to room temperature, heated at 110°C and reacted for 10h, then stopped heating, washed with water, filtered and evaporated. Dry, and purify by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 4.2 g of product (P84).
合成例(7):P96的合成Synthesis Example (7): Synthesis of P96
室温下,向500ml三口瓶中加入原料1(10g,44.27mmol),原料3(16.94g,44.27mmol),(DBA)3Pd2(0.81g,0.88mmol),三叔丁基膦四氟硼酸盐(0.51g,1.77mmol),叔丁醇钠(10.62g,110.68mmol),甲苯(100ml)作溶剂,置换三次氮气,升温至回流反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品18.2g(中间体8)。At room temperature, add raw material 1 (10g, 44.27mmol), raw material 3 (16.94g, 44.27mmol), (DBA) Pd (0.81g, 0.88mmol), tri-tert-butylphosphine tetrafluoroborate to a 500ml there-necked flask (0.51g, 1.77mmol), sodium tert-butoxide (10.62g, 110.68mmol), toluene (100ml) as solvent, nitrogen was replaced three times, heating was stopped after being heated to reflux for 12h, filtered and evaporated to dryness, purified by column chromatography (petroleum ether:dichloromethane=10:1) to obtain 18.2 g of product (intermediate 8).
室温下,向500ml三口瓶中加入中间体M8(18.2g,34.43mmol),原料7(9.62g,34.43mmol),Pd132(0.49g,0.69mmol),叔丁醇钠(8.26g,86.08mmol),二甲苯(200ml)作溶剂,置换三次氮气,升温至120℃反应12h后停止加热,过滤蒸干,柱层析提纯(石油醚:二氯甲烷=10:1),得到产品19.56g(中间体M9)。At room temperature, in a 500ml there-necked flask, add intermediate M8 (18.2g, 34.43mmol), raw material 7 (9.62g, 34.43mmol), Pd132 (0.49g, 0.69mmol), sodium tert-butoxide (8.26g, 86.08mmol) , xylene (200ml) was used as a solvent, nitrogen was replaced three times, the temperature was raised to 120 ° C and the reaction was stopped for 12h, then the heating was stopped, filtered and evaporated to dryness, and purified by column chromatography (petroleum ether: dichloromethane=10:1) to obtain 19.56g of the product (middle body M9).
将中间体M9(19.56g,37.01mmol)溶于200ml二甲苯中,在-40℃条件下缓慢滴加正丁基锂(44.41ml,111.03mmol),滴加完成后,恢复室温,在50℃条件下加热活化2h,后降温至-40℃,先后缓慢加入BBr3(23.13g,92.53mmol),和DIEA(19.10g,148.04mmol),恢复室温后加热110℃反应10h,后停止加热,水洗过滤蒸干,柱层析提纯(石油醚:二氯甲烷=20:1),得到产品8.6g(P96)。The intermediate M9 (19.56 g, 37.01 mmol) was dissolved in 200 ml of xylene, and n-butyllithium (44.41 ml, 111.03 mmol) was slowly added dropwise at -40 °C. It was heated and activated for 2 hours under the conditions, and then cooled to -40 °C. BBr3 (23.13 g, 92.53 mmol) and DIEA (19.10 g, 148.04 mmol) were slowly added successively. After returning to room temperature, the reaction was heated at 110 °C for 10 hours, and then the heating was stopped, washed with water and filtered. Evaporate to dryness, and purify by column chromatography (petroleum ether: dichloromethane=20:1) to obtain 8.6 g of product (P96).
分子结构理论计算Molecular Structure Theoretical Calculations
本发明采用Gaussian03对化合物进行量子化学计算,采用时间相关密度泛函方法分别对P1,P16,P29,P53,P54,P84,P96和C1,C2进行理论计算,计算结果如表1所示。In the present invention, Gaussian03 is used to perform quantum chemical calculation on the compound, and the time-dependent density functional method is used to perform theoretical calculation on P1, P16, P29, P53, P54, P84, P96 and C1, C2 respectively, and the calculation results are shown in Table 1.
其中,化合物C1和C2的结构式如下:Wherein, the structural formulas of compounds C1 and C2 are as follows:
表1Table 1
材料编号material code
|
第一单线态能级/eVFirst singlet energy level/eV
|
第一三线态能级/eVFirst triplet energy level/eV
|
第一单线态振子强度The first singlet oscillator strength
|
C1C1
|
3.053.05
|
2.57482.5748
|
0.17710.1771
|
C2C2
|
2.832.83
|
2.41662.4166
|
0.20960.2096
|
P1P1
|
3.073.07
|
2.57582.5758
|
0.21340.2134
|
P16P16
|
3.043.04
|
2.59172.5917
|
0.20730.2073
|
P29P29
|
3.033.03
|
2.58362.5836
|
0.20660.2066
|
P53P53
|
2.922.92
|
2.48622.4862
|
0.20350.2035
|
P54P54
|
3.013.01
|
2.59352.5935
|
0.21140.2114
|
P84P84
|
3.023.02
|
2.58452.5845
|
0.21020.2102
|
P96P96
|
2.992.99
|
2.58612.5861
|
0.20890.2089
|
材料的荧光发光波长与第一单线态能级相关,能级越高,材料的荧光发射波长越短,发光越偏蓝。材料的磷光发光波长与第一三线态能级相关,能级越高,材料的磷光发射波长越短,发光越偏蓝。材料的光致发光效率与第一单线态振子强度相关,第一单线态振子强度数值越大,材料发光效率越高。从计算结果可知本发明的材料在饱和六元环外稠合刚性芳环后,仍然可以保持较高的第一单线态能级和第一三线态能级,与参比材料C1相近。材料C1的激子能级与本发明化合物持平,但第一单线态振子强度相对较低,因而其发光效率可能相对较差。而材料C2在五元环外稠合芳环,实质上形成了一个大共轭结构,其第一单线态能级相对于本发明化合物较低,因而其发光波长可能较长,不能满足深蓝光器件的需要。The fluorescence emission wavelength of the material is related to the energy level of the first singlet state, and the higher the energy level, the shorter the fluorescence emission wavelength of the material, and the bluer the emission. The phosphorescence emission wavelength of the material is related to the energy level of the first triplet state, and the higher the energy level, the shorter the phosphorescence emission wavelength of the material, and the bluer the emission. The photoluminescence efficiency of the material is related to the intensity of the first singlet oscillator, and the larger the value of the first singlet oscillator intensity, the higher the luminous efficiency of the material. It can be seen from the calculation results that the material of the present invention can still maintain a relatively high first singlet state energy level and first triplet state energy level after condensing a rigid aromatic ring outside the saturated six-membered ring, which is similar to the reference material C1. The exciton energy level of the material C1 is the same as that of the compound of the present invention, but the intensity of the first singlet oscillator is relatively low, so its luminous efficiency may be relatively poor. The material C2 is fused with an aromatic ring outside the five-membered ring, which essentially forms a large conjugated structure, and its first singlet energy level is lower than that of the compound of the present invention, so its emission wavelength may be longer, which cannot meet the deep blue light. device needs.
器件实施例Device Embodiment
OLED包括位于第一电极和第二电极,以及位于电极之间的有机材料层。该有机材料又可以分为多个区域。比如,该有机材料层可以包括空穴传输区、发光层、电子传输区。The OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material can in turn be divided into multiple regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
在具体实施例中,在第一电极下方或者第二电极上方可以使用基板。基板均为具有机械强度、热稳定性、防水性、透明度优异的玻璃或聚合物材料。此外,作为显示器用的基板上也可以带有薄膜晶体管(TFT)。In particular embodiments, a substrate may be used under the first electrode or over the second electrode. The substrates are glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. In addition, a thin film transistor (TFT) may be provided on a substrate as a display.
第一电极可以通过在基板上溅射或者沉积用作第一电极的材料的方式来形成。当第一电极作 为阳极时,可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO
2)、氧化锌(ZnO)等氧化物透明导电材料或它们的任意组合。第一电极作为阴极时,可以采用镁(Mg)、银(Ag)、铝(Al)、铝-锂(Al-Li)、钙(Ca)、镱(Yb)、镁-铟(Mg-In)、镁-银(Mg-Ag)等金属或合金,或者它们之间的任意组合。
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO) or any combination thereof can be used. When the first electrode is used as a cathode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In) can be used ), magnesium-silver (Mg-Ag) and other metals or alloys, or any combination between them.
有机材料层可以通过真空热蒸镀、旋转涂敷、打印等方法形成于电极之上。用作有机材料层的化合物可以为有机小分子、有机大分子或聚合物,或者它们的组合。The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing and other methods. The compound used as the organic material layer may be an organic small molecule, an organic macromolecule or a polymer, or a combination thereof.
空穴传输区位于阳极和发光层之间。空穴传输区可以为单层结构的空穴传输层(HTL),包括只含有一种化合物的单层空穴传输层和含有多种化合物的单层空穴传输层。空穴传输区也可以为包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)中的至少一层的多层结构;其中HIL位于阳极和HTL之间,EBL位于HTL与发光层之间。The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a hole transport layer (HTL) with a single-layer structure, including a single-layer hole-transport layer containing only one compound and a single-layer hole-transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL between the HTL and the light-emitting layer.
空穴传输区的材料可以选自、但不限于酞菁衍生物如CuPc、导电聚合物或含导电掺杂剂的聚合物如聚苯撑乙烯、聚苯胺/十二烷基苯磺酸(Pani/DBSA)、聚(3,4-乙撑二氧噻吩)/聚(4-苯乙烯磺酸盐)(PEDOT/PSS)、聚苯胺/樟脑磺酸(Pani/CSA)、聚苯胺/聚(4-苯乙烯磺酸盐)(Pani/PSS)、芳香胺衍生物如下面HT-1至HT-51所示的化合物;或者其任意组合。The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene vinylene, polyaniline/dodecylbenzenesulfonic acid (Pani /DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly( 4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below; or any combination thereof.
空穴注入层位于阳极和空穴传输层之间。空穴注入层可以是单一化合物材料,也可以是多种 化合物的组合。例如,空穴注入层可以采用上述HT-1至HT-51的一种或多种化合物,或者采用下述HI-1-HI-3中的一种或多种化合物;也可以采用HT-1至HT-51的一种或多种化合物掺杂下述HI-1-HI-3中的一种或多种化合物:The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of the above-mentioned HT-1 to HT-51, or use one or more compounds of the following HI-1-HI-3; HT-1 can also be used One or more compounds to HT-51 doped with one or more of the following HI-1-HI-3 compounds:
发光层包括可以发射不同波长光谱的发光染料(即掺杂剂,dopant),还可以同时包括主体材料(Host)。发光层可以是发射红、绿、蓝等单一颜色的单色发光层。多种不同颜色的单色发光层可以按照像素图形进行平面排列,也可以堆叠在一起而形成彩色发光层。当不同颜色的发光层堆叠在一起时,它们可以彼此隔开,也可以彼此相连。发光层也可以是能同时发射红、绿、蓝等不同颜色的单一彩色发光层。The light-emitting layer includes light-emitting dyes (ie dopant, dopant) that can emit different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochromatic light-emitting layer that emits a single color such as red, green, and blue. The monochromatic light-emitting layers of a plurality of different colors can be arranged in a plane according to a pixel pattern, or can be stacked together to form a colored light-emitting layer. When light-emitting layers of different colors are stacked together, they can be spaced from each other or connected to each other. The light-emitting layer may also be a single-color light-emitting layer capable of simultaneously emitting different colors such as red, green, and blue.
根据不同的技术,发光层材料可以采用荧光电致发光材料、磷光电致发光材料、热活化延迟荧光发光材料等不同的材料。在一个OLED器件中,可以采用单一的发光技术,也可以采用多种不同的发光技术的组合。这些按技术分类的不同发光材料可以发射同种颜色的光,也可以发射不同种颜色的光。According to different technologies, different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent light emitting materials can be used as materials for the light emitting layer. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different luminescent materials, classified by technology, can emit light of the same color, or they can emit light of different colors.
在本发明的一方面,发光层采用荧光电致发光的技术。其发光层荧光主体材料可以选自但不限于以下所罗列的BFH-1至BFH-17的一种或多种的组合。In one aspect of the present invention, the light-emitting layer adopts the technology of fluorescent electroluminescence. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, a combination of one or more of BFH-1 to BFH-17 listed below.
在本发明的一方面,发光层采用热活化延迟荧光发光的技术。其发光层主体材料选自但不限于上述PH-1至PH-85中的一种或多种的组合。In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence emission. The host material of the light-emitting layer is selected from but not limited to a combination of one or more of the above-mentioned PH-1 to PH-85.
在本发明的一方面,发光层采用热活化延迟荧光发光的技术。其发光层荧光掺杂剂可以选自但不限于以下所罗列的TDE1-TDE37的一种或多种的组合。In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence emission. Its light-emitting layer fluorescent dopant can be selected from, but not limited to, a combination of one or more of TDE1-TDE37 listed below.
本发明的一方面,电子阻挡层(EBL)位于空穴传输层与发光层之间。电子阻挡层可以采用但不限于上述HT-1至HT-51的一种或多种化合物,或者采用但不限于上述PH-47至PH-77的一种或多种化合物;也可以采用但不限于HT-1至HT-51的一种或多种化合物和PH-47至PH-77的一种或多种化合物的混合物。In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer can adopt, but is not limited to, one or more compounds of the above-mentioned HT-1 to HT-51, or one or more compounds of the above-mentioned PH-47 to PH-77; Limited to mixtures of one or more compounds from HT-1 to HT-51 and one or more compounds from PH-47 to PH-77.
OLED有机材料层还可以包括发光层与阴极之间的电子传输区。电子传输区可以为单层结构的电子传输层(ETL),包括只含有一种化合物的单层电子传输层和含有多种化合物的单层电子传输层。电子传输区也可以为包括电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)中的至少一层的多层结构。The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be an electron transport layer (ETL) with a single-layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).
本发明的一方面,电子传输层材料可以选自、但不限于以下所罗列的ET-1至ET-65的一种或多种的组合。In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, a combination of one or more of ET-1 to ET-65 listed below.
本发明的一方面,空穴阻挡层(HBL)位于电子传输层与发光层之间。空穴阻挡层可以采用、但不限于上述ET-1至ET-65的一种或多种化合物,或者采用、但不限于PH-1至PH-46中的一种或多种化合物;也可以采用、但不限于ET-1至ET-65的一种或多种化合物与PH-1至PH-46中的一种或多种化合物之混合物。In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds of the above-mentioned ET-1 to ET-65, or adopt, but not limited to, one or more compounds of PH-1 to PH-46; or A mixture of one or more compounds of ET-1 to ET-65 and one or more compounds of PH-1 to PH-46 is employed, but not limited to.
器件中还可以包括位于电子传输层与阴极之间的电子注入层,电子注入层材料包括但不限于以下罗列的一种或多种的组合:LiQ、LiF、NaCl、CsF、Li
2O、Cs
2CO
3、BaO、Na、Li、Ca、Mg、Yb。
The device may also include an electron injection layer between the electron transport layer and the cathode, and the material of the electron injection layer includes but is not limited to a combination of one or more of the following: LiQ, LiF, NaCl, CsF, Li 2 O, Cs 2 CO 3 , BaO, Na, Li, Ca, Mg, Yb.
以下实施例中有机电致发光器件制备过程如下:The preparation process of the organic electroluminescent device in the following examples is as follows:
实施例1Example 1
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理,在去离子水中冲洗,在丙酮:乙醇混合溶剂中超声除油,在洁净环境下烘烤至完全除去水份,用紫外光和臭氧清洗,并用低能阳离子束轰击表面;The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreasing in an acetone:ethanol mixed solvent, baked in a clean environment until the water was completely removed, and UV light was used. Light and ozone cleaning, and bombarding the surface with a beam of low-energy cations;
把上述带有阳极的玻璃基片置于真空腔内,抽真空至<1×10
-5Pa,在上述阳极层膜上按先后顺序真空热蒸镀10nm的HT-4:HI-3(97/3,w/w)混合物作为空穴注入层,60nm的化合物HT-4作为空穴传输层,5nm的化合物HT-14作为电子阻挡层;20nm的化合物BFH-4:P1(100:3,w/w)二元混合物作为发光层,5nm的ET-23作为空穴阻挡层,25nm的化合物ET-61:ET-57(50/50,w/w)混合物作为电子传输层,1nm的LiF作为电子注入层,150nm的金属铝作为阴极。所有有机层和LiF的蒸镀总速率控制在0.1nm/秒,金属电极的蒸镀速率控制在1nm/秒。
The above-mentioned glass substrate with anode is placed in a vacuum chamber, evacuated to <1 × 10 -5 Pa, and 10nm of HT-4:HI-3 (97 nm) is vacuum thermally evaporated on the above-mentioned anode layer film in sequence. /3, w/w) mixture as hole injection layer, 60nm compound HT-4 as hole transport layer, 5nm compound HT-14 as electron blocking layer; 20nm compound BFH-4:P1 (100:3, w/w) binary mixture as emissive layer, 5 nm ET-23 as hole blocking layer, 25 nm mixture of compound ET-61:ET-57 (50/50, w/w) as electron transport layer, 1 nm LiF As the electron injection layer, metal aluminum of 150 nm was used as the cathode. The total evaporation rate of all organic layers and LiF was controlled at 0.1 nm/sec, and the evaporation rate of metal electrodes was controlled at 1 nm/sec.
实施例2~22以及对比例1~2Examples 2 to 22 and Comparative Examples 1 to 2
除了将实施例1中的P1分别替换为表2中相应的化合物之外,与实施例1相同地得到实施例2~9以及对比例1~2(分别将P1替换为化合物C1和C2)的有机电致发光器件。Except for replacing P1 in Example 1 with the corresponding compounds in Table 2, the same procedure as in Example 1 was carried out to obtain Examples 2 to 9 and Comparative Examples 1 to 2 (respectively replaced P1 with compounds C1 and C2). Organic Electroluminescent Devices.
对由上述过程制备的有机电致发光器件进行如下性能测定:The following performance measurements were performed on the organic electroluminescent devices prepared by the above process:
在同样亮度下,使用数字源表及亮度计测定实施例1~22以及对比例1~2中制备得到的有机电致发光器件的驱动电压和外量子效率(EQE)。具体而言,以每秒0.1V的速率提升电压,测定当有机电致发光器件的亮度达到1000cd/m
2时的电压即驱动电压,同时测出此时的外量子效率。
Under the same brightness, the driving voltage and external quantum efficiency (EQE) of the organic electroluminescent devices prepared in Examples 1-22 and Comparative Examples 1-2 were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1V per second, the voltage when the luminance of the organic electroluminescence device reached 1000cd/m 2 , that is, the driving voltage, was measured, and the external quantum efficiency at this time was also measured.
表2:本发明化合物与现有技术化合物作为空穴传输材料时所制备的器件性能比较Table 2: Comparison of device performance between the compounds of the present invention and prior art compounds as hole transport materials
器件实施例编号Device Example Number
|
化合物编号Compound number
|
电压VVoltage V
|
EQE(%)EQE(%)
|
光色light color
|
对比例1Comparative Example 1
|
C1C1
|
5.45.4
|
5.55.5
|
深蓝光deep blue light
|
对比例2Comparative Example 2
|
C2C2
|
5.25.2
|
6.86.8
|
天蓝光sky blue
|
实施例1Example 1
|
P1P1
|
4.74.7
|
6.96.9
|
深蓝光deep blue light
|
实施例2Example 2
|
P16P16
|
4.54.5
|
6.76.7
|
深蓝光deep blue light
|
实施例3Example 3
|
P29P29
|
4.94.9
|
6.26.2
|
深蓝光deep blue light
|
实施例4Example 4
|
P36P36
|
4.54.5
|
6.76.7
|
深蓝光deep blue light
|
实施例5Example 5
|
P44P44
|
4.34.3
|
6.96.9
|
深蓝光deep blue light
|
实施例6Example 6
|
P53P53
|
4.44.4
|
6.56.5
|
深蓝光deep blue light
|
实施例7Example 7
|
P54P54
|
4.84.8
|
6.56.5
|
深蓝光deep blue light
|
实施例8Example 8
|
P84P84
|
4.54.5
|
6.56.5
|
深蓝光deep blue light
|
实施例9Example 9
|
P96P96
|
4.74.7
|
6.66.6
|
深蓝光deep blue light
|
实施例10Example 10
|
P155P155
|
4.54.5
|
6.86.8
|
深蓝光deep blue light
|
实施例11Example 11
|
P159P159
|
4.54.5
|
6.66.6
|
深蓝光deep blue light
|
实施例12Example 12
|
P181P181
|
4.84.8
|
6.46.4
|
深蓝光deep blue light
|
实施例13Example 13
|
P182P182
|
4.64.6
|
6.66.6
|
深蓝光deep blue light
|
实施例14Example 14
|
P183P183
|
4.24.2
|
6.76.7
|
深蓝光deep blue light
|
实施例15Example 15
|
P184P184
|
4.54.5
|
6.36.3
|
深蓝光deep blue light
|
实施例16Example 16
|
P186P186
|
4.34.3
|
6.36.3
|
深蓝光deep blue light
|
实施例17Example 17
|
P187P187
|
4.94.9
|
6.46.4
|
深蓝光deep blue light
|
实施例18Example 18
|
P188P188
|
4.84.8
|
6.06.0
|
深蓝光deep blue light
|
实施例19Example 19
|
P189P189
|
5.05.0
|
6.26.2
|
深蓝光deep blue light
|
实施例20Example 20
|
P190P190
|
4.84.8
|
5.95.9
|
深蓝光deep blue light
|
实施例21Example 21
|
P191P191
|
4.94.9
|
6.06.0
|
深蓝光deep blue light
|
实施例22Example 22
|
P192P192
|
4.94.9
|
6.16.1
|
深蓝光deep blue light
|
以上结果表明,相对于参比材料C1,本发明的B-N类有机材料用于有机电致发光器件,由于其具更强的刚性结构,也具有更好的载流子传输性能,这些有助于其在OLED器件中表现出更高的外量子效率以及更低的电压。相对于参比材料C2,本发明的B-N类有机材料用于有机电致发光器件具有更加偏蓝的光色。据推测这是因为C2不具备本发明化合物中式(1)所示的基团,因此其用于有机电致发光器件时,发出的是天蓝光(470nm-490nm),而得不到深蓝光。此外,相较于参比材料,本发明的化合物所具有的更大的稠合刚性环结构有利于分子的近平面排列,这有利于光取出,从而提升其外量子效率。The above results show that, compared with the reference material C1, the BN-based organic material of the present invention is used in organic electroluminescence devices, because of its stronger rigid structure, it also has better carrier transport properties, which is helpful for It exhibits higher external quantum efficiency and lower voltage in OLED devices. Compared with the reference material C2, the B-N organic material of the present invention has a more bluish light color when used in an organic electroluminescent device. It is presumed that this is because C2 does not have the group represented by the formula (1) in the compound of the present invention, so when it is used in an organic electroluminescent device, it emits sky blue light (470nm-490nm) and cannot obtain deep blue light. In addition, compared with the reference material, the larger fused rigid ring structure of the compound of the present invention is favorable for the near-planar arrangement of molecules, which is favorable for light extraction, thereby improving its external quantum efficiency.
实施例12~15的有机电致发光器件的性能优于对比例1,但比起实施例1而言略有不足。具体而言,实施例1的有机电致发光器件的发光层染料采用了本发明的化合物P1,其X
1和X
2均为NR
3,而实施例12~15的有机电致发光器件采用的化合物为P181~P184,其X
1和X
2分别为CR
1R
2、 O、S和SiR
4R
5。由以上结果可知,就器件的外量子效率而言,使用了P1的实施例1>使用了P182的实施例13≈使用了P183的实施例14>使用了P181的实施例12≈使用了P184的实施例15。这可能是由于通过亚胺基将特定的芳香基团连接至母核的同时打断母核与该基团之间的共轭结构得到的本发明通式(1)的化合物,其第一单线态振子强度相对较高,因此表现出较高的外量子效率。
The performance of the organic electroluminescent devices of Examples 12 to 15 is better than that of Comparative Example 1, but is slightly insufficient compared to Example 1. Specifically, the luminescent layer dye of the organic electroluminescence device of Example 1 adopts the compound P1 of the present invention, and X 1 and X 2 are both NR 3 , while the organic electroluminescence devices of Examples 12 to 15 adopt the compound P1 of the present invention. The compounds are P181-P184, wherein X 1 and X 2 are CR 1 R 2 , O, S and SiR 4 R 5 respectively. From the above results, it can be seen that in terms of the external quantum efficiency of the device, Example 1 using P1 > Example 13 using P182 ≈ Example 14 using P183 > Example 12 using P181 ≈ Example 12 using P184 Example 15. This may be due to the compound of the general formula (1) of the present invention obtained by connecting a specific aromatic group to the parent nucleus through an imine group while breaking the conjugated structure between the parent nucleus and the group, the first single line of the compound of the present invention is The state oscillator strength is relatively high and thus exhibits high external quantum efficiency.
尽管结合实施例对本发明进行了说明,但本发明并不局限于上述实施例,应当理解,在本发明构思的引导下,本领域技术人员可进行各种修改和改进,所附权利要求概括了本发明的范围。Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above-mentioned embodiments, and it should be understood that various modifications and improvements can be made by those skilled in the art under the guidance of the inventive concept. The appended claims summarize the scope of the present invention.