WO2021196274A1 - 一种荧光材料及其合成方法 - Google Patents

一种荧光材料及其合成方法 Download PDF

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WO2021196274A1
WO2021196274A1 PCT/CN2020/084673 CN2020084673W WO2021196274A1 WO 2021196274 A1 WO2021196274 A1 WO 2021196274A1 CN 2020084673 W CN2020084673 W CN 2020084673W WO 2021196274 A1 WO2021196274 A1 WO 2021196274A1
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atom
cyclic group
fluorescent material
synthesis method
atoms
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王煦
王彦杰
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武汉华星光电半导体显示技术有限公司
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Priority to US16/957,396 priority Critical patent/US20230114209A1/en
Priority to EP20859640.3A priority patent/EP4137490A1/en
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Definitions

  • This application belongs to the field of organic light-emitting materials, and specifically relates to a fluorescent material and a synthesis method thereof.
  • OLED light-emitting materials are traditional fluorescent materials. Since the ratio of singlet and triplet excitons in OLED is 1:3, traditional fluorescent materials can only use singlet excitons to emit light. Therefore, the OLDE theory of traditional fluorescent materials The internal quantum efficiency is 25%. Although in terms of theoretical research, organic fluorescent materials have made considerable progress. For example, Professor Adachi has developed thermally induced delayed fluorescent materials (TADF) to realize the intersystem of excitons from triplet to singlet state. In theoretical research, the internal quantum efficiency can reach 100% (Adv. Mater., 2009, 21, 4802), but the actual situation is not.
  • TADF thermally induced delayed fluorescent materials
  • the triplet transition It depends on the number of electrons transitioning from the singlet state to the ground state per unit time and the triplet transition The ratio of the number of electrons to the singlet state. If the triplet electron does not quickly cross to the singlet state, it will gradually return to the ground state in the form of heat generation, resulting in energy loss. And because the spectrum is too wide, the light color emitted is not pure, the luminous efficiency of the blue material is low, and the life is short, and the application of TADF material in the display field is limited.
  • OLED uses red, green, and blue organic light-emitting molecules to produce three primary colors and then display various colors.
  • blue light-emitting materials are difficult to inject due to their short light-emitting wavelength and wide energy band gap; and blue light materials are more difficult to inject due to their special characteristics.
  • the molecular structure and carrier mobility are relatively poor, coupled with the visual function of the cause, the luminous efficiency and lifetime of blue light materials are much lower than that of red and green light. Blue light performance has become an unavoidable shortcoming that affects OLED display.
  • fluorescent materials with TTA triple-triple annihilation
  • TTA triple-triple annihilation
  • the purpose of the present application is to provide a deep blue fluorescent material with TTA effect and a synthesis method thereof.
  • This application provides a fluorescent material, which has the structural formula shown in formula (1):
  • Y is N atom or B atom;
  • X 1 and X 2 are the same or different and are selected from C atom or Si atom;
  • R 1 , R 2 , R 3 , R 4 are the same or different, and are selected from hydrogen atom, alkyl group, Hydrocarbon aryl or heteroaryl;
  • R 5 , R 6 , R 7 and R 8 are the same or different and are selected from alkyl, hydrocarbon aryl or heteroaryl; or R 5 and R 6 form a cyclic group; or R 7 and R 8 form a cyclic group.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are selected from C6-C50 hydrocarbon aryl, heteroaryl, C1-C20 alkane Or R 5 and R 6 form a C6-C50 cyclic group; or R 7 and R 8 form a C6-C50 cyclic group.
  • the R 5 and R 6 form a C6-C50 cyclic group with an aryl substituent; or R 7 and R 8 form a C6-C50 cyclic group with an aryl substituent .
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are selected from the following structural formulas:
  • the cyclic group has heteroatoms, and the heteroatoms are selected from O atoms, S atoms, or N atoms.
  • the cyclic group is selected from the following structural formulas:
  • X is selected from one of C atoms and Si atoms.
  • the present application provides a method for synthesizing the fluorescent material as described above, which includes the following steps: making the reactant with the structural formula (2) undergo a ring-closing reaction under the action of a catalyst to obtain the fluorescent material;
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are selected from C6-C50 hydrocarbon aryl, heteroaryl, C1-C20 alkane Or R 5 and R 6 form a C6-C50 cyclic group; or R 7 and R 8 form a C6-C50 cyclic group.
  • the R 5 and R 6 form a C6-C50 cyclic group with an aryl substituent; or R 7 and R 8 form a C6-C50 cyclic group with an aryl substituent .
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are selected from the following structural formulas:
  • the cyclic group has heteroatoms, and the heteroatoms are selected from O atoms, S atoms, or N atoms.
  • the cyclic group is selected from the following structural formulas:
  • X is selected from one of C atoms and Si atoms.
  • the catalyst is an acid catalyst.
  • the catalyst is concentrated hydrochloric acid and glacial acetic acid
  • the present application provides an electroluminescent device, which includes a first electrode, a light-emitting layer, and a second electrode.
  • the light-emitting layer includes the fluorescent material.
  • This application connects two acridines in a plane to form a type of organic fluorescent material with a rigid planar structure, which can reduce molecular vibration and reduce the interaction between molecules and solvents or other solute molecules , Reduce the possibility of collision deactivation, make the fluorescent material have strong fluorescence characteristics, and improve the quantum efficiency of the material.
  • the fluorescent material provided in the present application can be applied to the light-emitting layer of an organic electroluminescent device.
  • the maximum external quantum efficiency of the prepared organic electroluminescent device can reach 16%, and the device efficiency is high.
  • the method for synthesizing the fluorescent material provided by this application has a simple process, avoids the use of rare metals, and has huge application prospects in the OLED field.
  • Fig. 1 is the fluorescence spectra of the target compounds of fluorescent materials provided in Examples 1 and 2 of the present application.
  • Example 2 is a schematic diagram of the structure of the electroluminescent device prepared in Example 3 of the present application.
  • alkyl refers to a group derived from an aliphatic hydrocarbon and includes linear, branched, or cyclic groups. In some embodiments, the alkyl group has from 1 to 20 carbon atoms.
  • aryl refers to a moiety derived from an aromatic compound.
  • a group “derived from” a compound refers to a group formed by removing one or more hydrogen or deuterium.
  • the aryl group can be a single ring or have multiple rings fused together or covalently linked.
  • hydrocarbon aryl refers to having only carbon atoms in one or more aromatic rings.
  • heteroaryl refers to having one or more heteroatoms in an aromatic ring.
  • the aryl, hydrocarbon aryl, or heteroaryl group has 6 to 50 carbon atoms; in some embodiments, the aryl, hydrocarbon aryl, or heteroaryl group has 6 to 30 carbon atoms.
  • Fluorescent material whose structural formula is formula (1)
  • Y is N atom or B atom;
  • X 1 and X 2 are the same or different and are selected from C atom or Si atom;
  • R 1 , R 2 , R 3 , R 4 are the same or different, and are selected from hydrogen atom, alkyl group, Hydrocarbon aryl or heteroaryl;
  • R 5 , R 6 , R 7 , and R 8 are the same or different, and are selected from alkyl, hydrocarbon aryl, heteroaryl; or R 5 and R 6 form a cyclic group; or R 7 and R 8 form a cyclic group.
  • the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7, and R 8 are selected from C6-C50 hydrocarbon aryl, heteroaryl, C1-C20 alkane Or the R 5 and R 6 form a C6-C50 cyclic group; or the R 7 and R 8 form a C6-C50 cyclic group.
  • the R 5 and R 6 form a substituted C6-C50 cyclic group; or R 7 and R 8 form a substituted C6-C50 cyclic group.
  • the R 5 and R 6 form a C6-C50 cyclic group with an aryl substituent; or R 7 and R 8 form a C6-C50 cyclic group with an aryl substituent .
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are selected from the following structural formulas:
  • the cyclic group has heteroatoms, and the heteroatoms are selected from O atoms, S atoms, or N atoms.
  • the cyclic group is selected from the following structural formulas:
  • X is selected from one of C atoms and Si atoms.
  • a method for synthesizing the fluorescent material includes the following steps: the reactant with the structural formula (2) undergoes a ring-closure reaction under the action of a catalyst, and is cooled, extracted, dried, and filtered. , Concentration, separation and purification to obtain the fluorescent material;
  • the catalyst is concentrated hydrochloric acid and glacial acetic acid
  • the volume ratio of the concentrated hydrochloric acid and glacial acetic acid is 100:1 to 1:100
  • the volume ratio of the amount of reactants to the concentrated hydrochloric acid is 0.01- 100mol/L.
  • heating or refluxing assists 12-48 hours during the reaction.
  • This embodiment provides a deep blue fluorescent material (target compound 1), the structural formula of which is shown in formula (1-a):
  • the synthetic route of target compound 1 is as follows:
  • the synthesis method includes the following steps: adding the reactant (6.99g, 10mmol) of formula (2-a), 5mL concentrated hydrochloric acid and 15mL glacial acetic acid into a 50mL reaction vessel, and then reacting at 120°C for 24h. After cooling, pour into ice water, add 1mol/L sodium bicarbonate aqueous solution to neutralize the acid, then repeatedly extract with dichloromethane (DCM) three times, wash three times with water, dry with anhydrous sodium sulfate, filter, and concentrate. Using 200-300 mesh silica gel column chromatography and petroleum ether/DCM (4:1, V/V) as eluent, 5.43 g of white solid target compound 1 was obtained with a yield of 82%. 1HRMS[M+H]+calcd.for C50H34N2:662.2722; found:662.2734.
  • This embodiment provides a deep blue fluorescent material (target compound 2), the structural formula of which is shown in formula (1-b):
  • the synthetic route of target compound 2 is as follows:
  • the target compounds 1 and 2 and the traditional fluorescent material (Ref) shown in formula (3) were subjected to photophysical testing and analysis.
  • the fluorescence emission spectrum is shown in Figure 1.
  • the electrochemical energy levels of target compounds 1 and 2 and Ref The measurement results of the target compounds 1 and 2 and the lowest singlet (S1) and lowest triplet (T1) energy levels (T1) and the energy level difference of the target compounds 1 and 2 and Ref, and the photoluminescence quantum efficiency PLQY are shown in Table 1 below.
  • PLQY is measured with the help of the Absolute PL Quantum Yield Measurement C9920-03G system of Hamamatsu Photonics.
  • the emission wavelength of target compound 1 is 455 nm
  • the emission wavelength of target compound 2 is 464 nm, both of which emit a good deep blue light.
  • N is an electron-donating atom
  • boron is an electron-withdrawing atom
  • the boron-nitrogen bond will cause a certain degree of separation of HOMO and LUMO in the entire molecule.
  • the N-N bond molecule has little effect on the spectrum due to its symmetrical structure, while the introduction of boron atoms will cause a small red shift in the spectrum.
  • the target compounds 1 and 2 have obvious triplet-triplet annihilation effects.
  • T1 is twice greater than S1, it ensures that the triplet-triplet annihilation can occur.
  • two triplet molecules reach a certain concentration, two triplet annihilations will occur.
  • Intermolecular triplet state-triplet state annihilation process one molecule transitions back to the ground state, while the other molecule is excited to a higher energy singlet excited state, and molecules with sufficient singlet excited states return to the ground state by radiation transition and emit at the same time Blu-ray.
  • the target compounds 1 and 2 Compared with the traditional fluorescent material Ref, the target compounds 1 and 2 have higher emission quantum efficiencies of 94% and 96%, respectively. This is due to their larger rigid planar structure, which can effectively inhibit non-radiative transitions. The radiation rate constant is improved, and the photoluminescence quantum yield of the material is improved. At the same time, nitrogen atoms and boron atoms can increase the probability of intersystem transition from singlet excited state to triplet excited state. The molecule of the fluorescent material contains nitrogen atoms.
  • nitrogen atoms Because nitrogen atoms have empty p orbitals, they can form p- ⁇ conjugation with the benzene ring, which enhances the conjugation degree of ⁇ electrons and makes the transition between the lowest excited singlet state and the ground state The probability is increased to promote efficient fluorescent light emission of fluorescent materials.
  • the boron atom in the target compound 2 has a highly electron-deficient structure and strong electron-attracting properties.
  • the nitrogen-boron bond has a high bond energy and a stable structure. It can form a class of fluorescent materials with high quantum efficiency and good light-emitting color TTA properties. .
  • This embodiment provides an organic electroluminescent device, as shown in FIG. 2, comprising a first electrode 11, a hole injection layer 12, a hole transport layer 13, a light emitting layer 14, and electrons arranged in sequence from bottom to top.
  • the first electrode 11 is a conductive glass (ITO) substrate
  • the hole injection layer 12 is HATCN
  • the hole transport layer 13 is NPB
  • the light-emitting layer 14 includes target compound 1 or 2 or traditional fluorescent material Ref as a guest material doped
  • the electron transport layer 15 is TPBI
  • the electron injection layer 16 is LiF
  • the second electrode 17 is Al.
  • the manufacturing method refers to Chem.Sci., 2016, 7, 4044-4051, to obtain
  • Target device 1
  • Target device 2
  • the current-brightness-voltage characteristics of the device are measured by the Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode.
  • the electroluminescence spectrum is measured by the French JY company SPEX CCD3000 spectrometer, all measurements All are done in the atmosphere at room temperature.
  • EL peak represents the strongest emission peak of the electroluminescence emission spectrum.
  • Table 2 Target devices 1 and 2 and the full width at half maximum of the emission spectra of the comparative devices, the strongest emission peak wavelength and the maximum external quantum efficiency.
  • the target devices 1 and 2 prepared by using the target compounds 1 and 2 as the light-emitting layer have good device performance.
  • the wavelengths of the strongest emission peaks are 458 nm and 461 nm, and the full width at half maximum is 37 nm and 32 nm, respectively, which proves that the emission color of target device 1 and target device 2 is blue.
  • the blue emission peak is narrow and the color purity is good.
  • the maximum external quantum efficiencies of the two are as high as 15% and 16%, respectively.
  • the fluorescent material as a guest material is doped in the host material as a light-emitting layer, which improves the light-emitting life of the device.
  • the above data fully shows that this type of fluorescent material with a plane structure containing nitrogen-nitrogen or nitrogen-boron bonds is feasible as a light-emitting material , It has good energy transfer with the host material, and it is a deep blue guest material with excellent performance.

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Abstract

一种荧光材料及其合成方法，所述荧光材料具有如下结构式：（I），其中，Y为N原子或B原子；X1和X2相同或不同并且选自C原子或Si原子；R1、R2、R3、R4相同或不同，选自氢原子、烷基、烃芳基或杂芳基；R5、R6、R7、R8相同或不同，选自烷基、烃芳基或杂芳基；或者R5和R6形成环状基团；或者R7和R8形成环状基团。

Description

一种荧光材料及其合成方法 技术领域
本申请属于有机发光材料领域，具体涉及一种荧光材料及其合成方法。
背景技术
随着OLED技术在显示和照明领域的不断发展，人们对其核心材料的研究将更加关注，特别是有机电致发光材料。早期的OLED发光材料为传统荧光材料，由于在OLED中单重态和三重态的激子比例为1:3，但传统荧光材料只能利用单重态激子发光，因此传统荧光材料的OLDE理论内量子效率为25％，虽然在理论研究方面，有机荧光材料已取得了长足的发展，比如Adachi教授开发了热致延迟荧光材料(TADF)，实现激子由三重态到单重态的系间跨越，理论研究上内部量子效率可以达到100％(Adv.Mater.,2009,21,4802)，但是实际情况并不是，这取决于单位时间内从单重态跃迁到基态电子数目和三重态跨越到单重态的电子数目的比例，如果三重态的电子不快速跨越到单重态，它就会逐渐以发热等形式回到基态，产生能量的损失。且由于光谱太宽，导致发出的光色不纯，蓝光材料的发光效率低，寿命较短，TADF材料在显示领域的应用受限。
OLED是由红、绿、蓝有机发光分子产生三基色进而显示各种颜色，其中蓝色发光材料由于其发光波长短，能量带隙宽，载流子注入比较困难；而且蓝光材料由于其特殊的分子结构，载流子迁移能力也相对较差，再加上视觉函数的原因，导致蓝光材料的发光效率和寿命远低于红光和绿光。蓝光性能成为影响OLED显示的一个无法避免的短板。目前，具有TTA(triple-triple annihilation)效应的荧光材料，由于电子在三重态的湮灭效应，提高单重态电子的总量，理论上的内量子效率可以达到62.5％，在显示领域也得到了广泛的关注，OLED显示领域对性能优异的蓝光发光材料的需求为对TTA性质的荧光材料的开发和设计提供了机遇和挑战。
技术问题
为了解决所述现有技术的问题和不足，本申请的目的在于提供一种具有 TTA效应的深蓝光荧光材料及其合成方法。
技术解决方案
本申请提供一种荧光材料，所述荧光材料具有式(1)所示的结构式：
Figure PCTCN2020084673-appb-000001
其中，Y为N原子或B原子；X 1和X 2相同或不同并且选自C原子或Si原子；R 1、R 2、R 3、R 4相同或不同，选自氢原子、烷基、烃芳基或杂芳基；R 5、R 6、R 7、R 8相同或不同，选自烷基、烃芳基或杂芳基；或者R 5和R 6形成环状基团；或者R 7和R 8形成环状基团。
在一些实施方式中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自C6-C50的烃芳基、杂芳基、C1-C20的烷基；或者R 5和R 6形成C6-C50的环状基团；或者R 7和R 8形成C6-C50的环状基团。
在一些实施方式中，所述R 5和R 6形成具有芳基取代基的C6-C50的环状基团；或者R 7和R 8形成具有芳基取代基的C6-C50的环状基团。
在一些实施方式中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
Figure PCTCN2020084673-appb-000002
在一些实施方式中，所述环状基团上具有杂原子，所述杂原子选自O原子、S原子或N原子。
在一些实施方式中，所述环状基团选自如下结构式：
Figure PCTCN2020084673-appb-000003
其中，X选自C原子和Si原子中的一种。
本申请提供一种合成如上所述的荧光材料的方法，包括以下步骤：使结构式为式(2)的反应物在催化剂作用下发生关环反应，获得所述荧光材料；
Figure PCTCN2020084673-appb-000004
在一些实施方式中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自C6-C50 的烃芳基、杂芳基、C1-C20的烷基；或者R 5和R 6形成C6-C50的环状基团；或者R 7和R 8形成C6-C50的环状基团。
在一些实施方式中，所述R 5和R 6形成具有芳基取代基的C6-C50的环状基团；或者R 7和R 8形成具有芳基取代基的C6-C50的环状基团。
在一些实施方式中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
Figure PCTCN2020084673-appb-000005
在一些实施方式中，所述环状基团上具有杂原子，所述杂原子选自O原子、S原子或N原子。
在一些实施方式中，所述环状基团选自如下结构式：
Figure PCTCN2020084673-appb-000006
其中，X选自C原子和Si原子中的一种。
在一些实施方式中，所述催化剂为酸催化剂。
在一些实施方式中，所述催化剂为浓盐酸和冰醋酸；反应时加热或回流辅
助12-48小时。
本申请提供一种电致发光器件，包括第一电极、发光层和第二电极，所述发光层包括所述荧光材料。
有益效果
(1)本申请将两个吖啶连接在一个平面内，形成一类具有刚性平面结构的有机荧光材料，所述刚性平面结构可以减少分子振动，使分子与溶剂或其它溶质分子的相互作用减少，减少了碰撞去活的可能性，使该荧光材料具有强烈的荧光特性，提高了材料的量子效率。
(2)本申请提供的荧光材料可以应用在有机电致发光器件的发光层中，制备的有机电致发光器件的最大外量子效率可达16％，器件效率高。
(3)本申请提供的荧光材料的合成方法工艺简单，避免稀有金属的使用，在OLED领域具有巨大的应用前景。
附图说明
图1是本申请实施例1和2提供的荧光材料目标化合物的荧光光谱。
图2是本申请实施例3制备的电致发光器件的结构示意图。
本发明的实施方式
具体实施方式首先提出术语的定义和阐明，然后是结构式为式(1)的深蓝光荧光材料，以及最后的实施例。
1、术语的定义和阐明
在提出下述实施例的详情之前，定义或阐明一些术语。
术语“烷基”是指衍生自脂肪族烃的基团并且包括直链、支链、或环状基团。在一些实施例中，烷基具有从1到20的碳原子。
术语“芳基”是指衍生自芳香族化合物的部分。“衍生自”化合物的基团表示通过除去一个或多个氢或氘形成的基团。芳基可以是单个环或具有稠合在一起或共价连接的多个环。
术语“烃芳基”是指在一个或多个芳环中仅具有碳原子。
术语“杂芳基”是指在一个芳环中具有一个或多个杂原子。
在一些实施例中，芳基、烃芳基或杂芳基具有6至50个碳原子；在一些实施例中，芳基、烃芳基或杂芳基具有6至30个碳原子。
所有基团可以是取代或未经取代的。
除非另有定义，否则在此所使用的所有技术和科学术语均具有与本申请所属领域普通技术人员所通常理解的相同含义。尽管与在此所述的那些类似或等 同的方法和材料可以用于本申请实施例的实践或测试中，但在以下描述适合的方法和材料。此外，材料、方法和实施例仅仅是示例性的并且不旨在是限制性的。
2、结构式为式(1)的荧光材料
在此描述的荧光材料的结构式为式(1)所示：
Figure PCTCN2020084673-appb-000007
其中，Y为N原子或B原子；X 1和X 2相同或不同并且选自C原子或Si原子；R 1、R 2、R 3、R 4相同或不同，选自氢原子、烷基、烃芳基或杂芳基；R 5、R 6、R 7、R 8相同或不同，选自烷基、烃芳基、杂芳基；或者R 5和R 6形成环状基团；或者R 7和R 8形成环状基团。
在一些实施例中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自C6-C50的烃芳基、杂芳基，C1-C20的烷基；或者所述R 5和R 6形成C6-C50的环状基团；或者所述R 7和R 8形成C6-C50的环状基团。
在一些实施例中，所述R 5和R 6形成具有取代基的C6-C50的环状基团；或者R 7和R 8形成具有取代基的C6-C50的环状基团。
在一些实施例中，所述R 5和R 6形成具有芳基取代基的C6-C50的环状基团；或者R 7和R 8形成具有芳基取代基的C6-C50的环状基团。
在一些实施例中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
Figure PCTCN2020084673-appb-000008
在一些实施例中，所述环状基团上具有杂原子，杂原子选自O原子、S原子或N原子。
在一些实施例中，所述环状基团选自如下结构式：
Figure PCTCN2020084673-appb-000009
其中，X选自C原子和Si原子的一种。
在一些实施例中，还描述了一种合成所述的荧光材料的方法，包括以下步骤：结构式为式(2)的反应物在催化剂作用下发生关环反应，经冷却、萃取、干燥、过滤、浓缩、分离提纯，得所述荧光材料；
Figure PCTCN2020084673-appb-000010
在一些实施例中，所述催化剂为浓盐酸和冰醋酸，所述浓盐酸和冰醋酸的 体积比为100:1-1：100，反应物的物质的量与浓盐酸的体积比为0.01-100mol/L。
在一些实施例中，反应时加热或回流辅助12-48小时。
3、以下结合具体实施例1至6和附图对本申请的具体实施作进一步说明，但本申请的实施不限于此。
实施例1
本实施例提供了一种深蓝光荧光材料(目标化合物1)，其结构式如式(1-a)所示：
Figure PCTCN2020084673-appb-000011
目标化合物1的合成路线如下所示：
Figure PCTCN2020084673-appb-000012
合成方法包括以下步骤：将结构式为式(2-a)的反应物(6.99g，10mmol)、5mL浓盐酸和15mL冰醋酸加入到50mL的反应容器中，然后在120℃下反应24h。冷却后，倒入冰水中，加入1mol/L的碳酸氢钠水溶液中和酸，然后用二氯甲烷(DCM)反复萃取三次，水洗三次，无水硫酸钠干燥，过滤，浓缩。用200-300目的硅胶柱层析，石油醚/DCM(4:1，V/V)作为淋洗剂，得到5.43g白色固体目标化合物1，收率82％。1HRMS[M+H]+calcd.for C50H34N2:662.2722；found:662.2734。
Figure PCTCN2020084673-appb-000013
实施例2
本实施例提供了一种深蓝光荧光材料(目标化合物2)，其结构式如式(1-b)所示：
Figure PCTCN2020084673-appb-000014
目标化合物2的合成路线如下所示：
Figure PCTCN2020084673-appb-000015
将结构式如式(2-b)的反应物(6.99g，10mmol)、5mL浓盐酸和15mL冰醋酸加入到50mL的反应容器中，然后120℃反应24h。冷却后，倒入冰水中，加入1mol/L的碳酸氢钠水溶液中和酸，然后用二氯甲烷(DCM)反复萃取三次，水洗三次，无水硫酸钠干燥，过滤，浓缩。用200-300目的硅胶柱层析，石油醚/DCM(4:1，V/V)作为淋洗剂，得到5.43g白色固体目标化合物2， 收率82％。1HRMS[M+H]+calcd.for C50H34BN:659.2784；found:659.2798。
实施例3
对目标化合物1和2以及结构式如式(3)所示的传统荧光材料(Ref)进行光物理测试分析，荧光发射光谱如图1所示；对目标化合物1和2以及Ref的电化学能级等参数进行测定，目标化合物1和2以及Ref的最低单重态(S1)和最低三重态能级(T1)及其能级差，和光致发光量子效率PLQY的测试结果如下表1所示。
Figure PCTCN2020084673-appb-000016
S1通过室温荧光光谱测定，T1通过低温(77K)磷光光谱测定，HOMO与LUMO通过电化学氧化还原测定。光致发光光谱(photoluminescence，简称PL光谱)，PL peak是指光致发光光谱的最强发射峰；PLQY的测量时借助于Hamamatsu Photonics公司的Absolute PL Quantum Yield Measurement C9920-03G系统进行。PLQY也叫荧光效率或量子效率，它表示物质发射荧光、的能力，通常用下式表示：PLQY％＝发射荧光分子数/激发分子总数。
表1目标化合物1和2以及Ref的最低单重态(S1)和最低三重态能级(T1)及其能级差，和PLQY测试结果。
Figure PCTCN2020084673-appb-000017
由图1和表1可知，目标化合物1的发射波长为455nm，目标化合物2 的发射波长为464nm，均发出较好的深蓝光。又由于N是给电子原子，硼是吸电子原子，硼氮键会使得整个分子出现一定程度的HOMO和LUMO的分离。N-N键分子由于结构对称，对光谱影响不大，而硼原子的引入会使得光谱少量红移。
目标化合物1和2具有明显的三重态-三重态湮灭效应，当2倍的T1大于S1，确保了三重态-三重态湮灭能够发生，两个三重态的分子达到一定浓度，就会发生两个分子间的三重态-三重态湮灭过程，一个分子跃迁回基态，而另一个分子被激发到能级更高的单重激发态，充裕单重激发态的分子以辐射跃迁方式退回基态，同时发出蓝光。
和传统的荧光材料Ref相比，目标化合物1和2具有较高的发光量子效率，分别为94％和96％，这得益于他们的较大的刚性平面结构，能够有效抑制非辐射跃迁，提高了辐射速率常数，进而提供提高材料的光致发光量子产率，同时氮原子和硼原子能够提高单线态激发态到三线态激发态的系间窜跃几率。该荧光材料的分子含有氮原子，由于氮原子具有空的p轨道，可以和苯环形成p-π共轭，增强了π电子的共轭程度，使最低激发单重态与基态之间的跃迁几率增大，促进荧光材料高效荧光发光。目标化合物2中的硼原子使高缺电子结构，具有很强的吸电子性质，氮-硼键键能较高，结构稳定，可形成一类量子效率高、发光颜色好的TTA性质的荧光材料。
实施例4
本实施例提供了一种有机电致发光器件，如图2所示，包括从下到上依次排布的第一电极11、空穴注入层12、空穴传输层13、发光层14、电子传输层15、电子注入层16和第二电极17。所述第一电极11为导电玻璃(ITO)衬底，空穴注入层12为HATCN，空穴传输层13为NPB，发光层14包括目标化合物1或2或传统荧光材料Ref作为客体材料掺杂的发光材料，电子传输层15为TPBI，电子注入层16为LiF，第二电极17为Al，制作方法参照Chem.Sci.,2016,7,4044-4051，得到
目标器件1：
ITO(150nm)/HATCN(10nm)/NPB(20nm)/host:(2％)化合物1(30nm)/TPBI(10nm)/LiF(1nm)/Al(100nm)；
目标器件2：
ITO(150nm)/HATCN(10nm)/NPB(20nm)/host:(2％)化合物2(30nm)/TPBI(10nm)/LiF(1nm)/Al(100nm)；
对比器件：
ITO(150nm)/HATCN(10nm)/NPB(20nm)/host:(2％)Ref(30nm)/TPBI(10nm)/LiF(1nm)/Al(100nm)。
对目标器件1和2以及对比器件的性能进行测试。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源测量系统(Keithley 2400Sourcemeter、Keithley 2000Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。
测试结果如表2所示。电致发光(EL:Electroluminescence)发射光谱，EL peak表示电致发光发射光谱的最强发射峰。
表2目标器件1和2以及对比器件的发射光谱的半峰全宽、最强发射峰波长和最大外量子效率。
Figure PCTCN2020084673-appb-000018
由表2可知，和对比器件相比，由目标化合物1和2作为发光层，制备的目标器件1和2具有良好的器件性能。最强发射峰的波长分别为458nm和461nm，半峰全宽分别为37nm和32nm，证明目标器件1和目标器件2的发光颜色是蓝光。蓝色发射峰较窄，色纯度好，两者的最大外部量子效率分别高达15％和16％，对比目标器件1和2与对比器件在1000cd/m 2下的使用寿命，以本申请所提供的荧光材料作为客体材料掺杂在主体材料中作为发光层，提高了器件的发光寿命，以上数据充分表明此类含有氮-氮或氮-硼键的平面结构的荧光材料作为发光材料是可行的，与主体材料具有良好的能量转移，是性能优异的深蓝光客体材料。
综上所述，虽然本申请已以优选实施例揭露如上，但上述优选实施例并非用以限制本申请，本领域的普通技术人员，在不脱离本申请的精神和范围内，均可作各种更动与润饰，因此本申请的保护范围以权利要求界定的范围为准。

Claims (16)

  1. 一种荧光材料，其中，所述荧光材料具有式(1)所示的结构式：
    Figure PCTCN2020084673-appb-100001
    其中，Y为N原子或B原子；X 1和X 2相同或不同并且选自C原子或Si原子；R 1、R 2、R 3、R 4相同或不同，选自氢原子、烷基、烃芳基或杂芳基；R 5、R 6、R 7、R 8相同或不同，选自烷基、烃芳基或杂芳基；或者R 5和R 6形成环状基团；或者R 7和R 8形成环状基团。
  2. 根据权利要求1所述的荧光材料，其中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自C6-C50的烃芳基、杂芳基、C1-C20的烷基；或者R 5和R 6形成C6-C50的环状基团；或者R 7和R 8形成C6-C50的环状基团。
  3. 根据权利要求2所述的荧光材料，其中，所述R 5和R 6形成具有芳基取代基的C6-C50的环状基团；或者R 7和R 8形成具有芳基取代基的C6-C50的环状基团。
  4. 根据权利要求1所述的荧光材料，其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
    Figure PCTCN2020084673-appb-100002
  5. 根据权利要求2所述的荧光材料，其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
    Figure PCTCN2020084673-appb-100003
  6. 根据权利要求1所述的荧光材料，其中，所述环状基团上具有杂原子，所述杂原子选自O原子、S原子或N原子。
  7. 根据权利要求1所述的荧光材料，其中，所述环状基团选自如下结构式：
    Figure PCTCN2020084673-appb-100004
    其中，X选自C原子和Si原子中的一种。
  8. 一种合成如权利要求1所述的荧光材料的方法，其中，包括以下步骤：使结构式为式(2)的反应物在催化剂作用下发生关环反应，获得所述荧光材料；
    Figure PCTCN2020084673-appb-100005
  9. 根据权利要求8所述的合成方法，其中，所述R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自C6-C50的烃芳基、杂芳基、C1-C20的烷基；或者R 5和R 6形成C6-C50的环状基团；或者R 7和R 8形成C6-C50的环状基团。
  10. 根据权利要求8所述的合成方法，其中，所述R 5和R 6形成具有芳基取代基的C6-C50的环状基团；或者R 7和R 8形成具有芳基取代基的C6-C50的环状基团。
  11. 根据权利要求8所述的合成方法，其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8选自如下的结构式：
    Figure PCTCN2020084673-appb-100006
  12. 根据权利要求8所述的合成方法，其中，所述环状基团上具有杂原子，所述杂原子选自O原子、S原子或N原子。
  13. 根据权利要求8所述的合成方法，其中，所述环状基团选自如下结构式：
    Figure PCTCN2020084673-appb-100007
    其中，X选自C原子和Si原子中的一种。
  14. 根据权利要求8所述的合成方法，其中，所述催化剂为酸催化剂。
  15. 根据权利要求8所述的合成方法，其中，所述催化剂为浓盐酸和冰醋酸；反应时加热或回流辅助12-48小时。
  16. 一种电致发光器件，包括第一电极、发光层和第二电极，其中，所述发光层包括如权利要求1所述的荧光材料。
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