WO2020103294A1 - 有机小分子发光材料及有机电致发光器件 - Google Patents

有机小分子发光材料及有机电致发光器件

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WO2020103294A1
WO2020103294A1 PCT/CN2018/124982 CN2018124982W WO2020103294A1 WO 2020103294 A1 WO2020103294 A1 WO 2020103294A1 CN 2018124982 W CN2018124982 W CN 2018124982W WO 2020103294 A1 WO2020103294 A1 WO 2020103294A1
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organic
light
adamantane
small molecule
organic electroluminescent
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French (fr)
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吴元均
矫士博
史婷
苏仕健
李伟
李彬彬
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/20—Spiro-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Definitions

  • the invention relates to the field of organic electroluminescence, in particular to an organic small molecule luminescent material and an organic electroluminescent device using the organic small molecule luminescent material.
  • OLED Organic electroluminescence
  • the principle of the organic electroluminescent device is that under the action of an electric field, holes and electrons are injected from the anode and the cathode, respectively, through the hole injection layer, the hole transport layer and the electron injection layer, the electron transport layer, formed in the light-emitting layer recombination Excitons, exciton radiation decays and glows.
  • organic electroluminescent materials As the core component of organic electroluminescent devices, organic electroluminescent materials have a great influence on the performance of the devices. Among them, high quantum efficiency fluorescence characteristics, good semiconductor characteristics, high-quality film-forming characteristics, good chemical stability and thermal stability, good processing performance, etc. are its main performance factors. According to the molecular structure characteristics, it is classified according to the emission wavelength range, including organic small molecule light-emitting materials, organic complex light-emitting materials and organic polymer light-emitting materials.
  • organic complex luminescent materials are basically heavy metal complexes, the production cost is high, which is not conducive to large-scale production, and there is a serious efficiency roll-off phenomenon in organic complex luminescent materials under high current density
  • the stability of the organic complex luminescent materials is not good, and compared with polymer materials, organic small molecule luminescent materials have fewer preparation steps, stable structure, and convenient purification, so they can obtain higher device efficiency , So that it is more likely to be commercialized.
  • flexible OLED devices made with small organic light-emitting materials have received great attention because of their unparalleled advantages, and have made tremendous progress.
  • Organic light-emitting diodes have made great progress so far, and scientists have proposed various theories to explain the mechanism of light emission.
  • organic small-molecule photoelectric materials with simple structures, good performance, and commercialization requirements are still very limited, and the development of new organic photoelectric materials still has a pivotal significance.
  • the object of the present invention is to provide a small organic light-emitting material that has a very high photoluminescence quantum yield in a thin-film state and is a light-emitting guest material with good electron-hole dual-transport properties.
  • Another object of the present invention is to provide an organic electroluminescent device.
  • the light-emitting layer uses the above-mentioned organic small molecule light-emitting material, which has high external quantum efficiency and excellent light-emitting performance.
  • the present invention provides a small organic light-emitting material using 10H-spiro [acridine-9,2'-adamantane] as the donor unit, which is obtained by coupling the acceptor unit and the donor unit Of luminescent materials;
  • Ar is an aromatic substituent having electron-deficient properties.
  • the organic small molecule luminescent material consists of 2,4,6-triphenyltriazine, 2,4,6-triphenylpyrazine, 1,3-phthalonitrile and 3,5-phthalonitrile , Diphenylphosphono, diphenylsulfone, phenoxazine-10,10'-dioxide, tris (2,6-xylyl) boron, thioanthracene-5,5,10,10-tetraoxide
  • the substance, 9-thioxanthone or 9-zanthone is the acceptor unit.
  • the small organic light-emitting material is prepared by the donor unit 10H-spiro [acridine-9,2'-adamantane] and the acceptor unit as raw materials through a Hartwig-Buchwald coupling reaction.
  • 10H-spiro [acridine-9,2'-adamantane] is prepared from aniline, o-bromoiodobenzene and adamantone, which are prepared by Hartwig-Buchwald coupling reaction and (Boc) 2 O plus protection reaction in this order .
  • the present invention also provides an organic electroluminescent device, which includes a light-transmitting substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer that are stacked;
  • the light emitting layer contains the organic small molecule light emitting material as described above.
  • the small organic light-emitting material serves as a light-emitting guest material in the light-emitting layer.
  • the light-emitting layer includes one or more of the organic small molecule light-emitting materials having different structural formulas.
  • the light-emitting layer is prepared by thermal evaporation, spin coating, brush coating, spray coating, dip coating, roll coating, printing, or inkjet printing.
  • the organic small molecule luminescent material of the present invention is composed of a novel acridine donor unit 10H-spiro [cridine-9,2'-adamantane] based on a non-aromatic rigid structure adamantane, Coupling with the acceptor unit, its structure is single, the molecular weight is determined, it is easy to purify, and the reproducibility of multiple synthesis is good, with a low sublimation temperature and a high decomposition temperature, the film morphology is stable, due to the donor unit 10H-spiro [ Acridine-9,2'-adamantane] has a very rigid structure, a non-aromatic rigid structure adamantane as part of the donor structure, this small organic light-emitting material has a very high photoluminescence quantum yield in the state of thin film Rate, when used in organic electroluminescent devices, it can effectively solve the problem of low efficiency of excited molecules due to configuration relaxation resulting in severe non-radi
  • FIG. 1 is a thermogravimetric analysis diagram of molecule 1 prepared in Example 7;
  • Figure 2 is the absorption spectra of molecules 1, 2, 3 and 4 prepared in Examples 7, 8, 9 and 10 in toluene solution;
  • FIG. 3 is a fluorescence emission spectrum of molecules 1, 2, 3, and 4 prepared in Examples 7, 8, 9, and 10 in a toluene solution;
  • Example 4 is a graph of current density-voltage-luminance curve of an organic electroluminescent device using molecule 1 prepared in Example 7 as a guest material of a light-emitting layer;
  • Example 5 is a graph of current efficiency-luminance relationship of an organic electroluminescent device using molecule 1 prepared in Example 7 as a guest material of a light-emitting layer;
  • Example 6 is a graph showing the relationship between the external quantum efficiency and brightness of an organic electroluminescent device using the molecule 1 prepared in Example 7 as a guest material of a light-emitting layer;
  • Example 7 is a light emission spectrum of an organic electroluminescence device using molecule 1 prepared in Example 7 as a guest material of a light emitting layer;
  • 10 is a graph showing the relationship between the external quantum efficiency and the brightness of an organic electroluminescent device using the compound DMAc-TRZ as the light-emitting layer guest material;
  • FIG. 11 is a light emission spectrum of an organic electroluminescence device using the compound DMAc-TRZ as a guest material of a light emitting layer.
  • the invention provides an organic small molecule luminescent material, adopting a new type of acridine donor unit 10H-spiro [cridine-9,2'-adamantane] based on non-aromatic rigid structure adamantane, through Hartwig- Buchwald coupling reaction luminescent material obtained by coupling the donor unit 10H-spiro [acridine-9,2'-adamantane] with the acceptor unit.
  • 10H-spiro [acridine-9,2'-adamantane] is obtained through a series of simple reactions such as Hartwig-Buchwald reaction, (Boc) 2 O plus protection reaction, low temperature reaction, normal temperature or high temperature ring closure reaction, Its chemical structural formula is
  • adamantane Since the inherent rigid structure of adamantane can increase the rigidity of the entire molecule, it can effectively reduce the energy loss caused by the geometric configuration deformation of the small organic light-emitting molecule composed of it in the excited state, so the donor unit 10H is used -
  • the organic small molecule luminescent material obtained by spiro [acridine-9,2'-adamantane] has a very high photoluminescence quantum yield in a thin film state, which in turn helps to improve the efficiency and stability of the device.
  • Ar is an aromatic substituent having electron-deficient properties.
  • the small organic light-emitting material is 2,4,6-triphenyltriazine, 2,4,6-triphenylpyrazine, 1,3-phthalonitrile, 3,5-benzene Dicarbonitrile, diphenylphosphono, diphenylsulfone, phenoxazine-10,10'-dioxide, tris (2,6-xylyl) boron, thioanthracene-5,5,10,10 -Commonly used electron-deficient aromatic compounds and their derivatives such as tetraoxide, 9-thioxanthone, or 9-zanthone are receptor units.
  • Ar may be any organic radical
  • the organic small molecule luminescent material of the present invention consists of a novel acridine donor unit 10H-spiro [cridine-9,2'-adamantane] based on a non-aromatic rigid structure adamantane, coupled with an acceptor unit It has a single structure, a fixed molecular weight, is easy to purify, and has good reproducibility for multiple synthesis. It has a low sublimation temperature and a high decomposition temperature, and the film morphology is stable.
  • the organic small molecule luminescent material obtained by using the donor unit has a very high photoluminescence quantum in the thin film state Yield, when used in organic electroluminescent devices, can effectively solve the problem of low efficiency of the excited state molecules due to configuration relaxation resulting in severe non-radiative attenuation, and can be changed by changing the , 2'-adamantane]
  • the type of acceptor unit connected can adjust the material's luminous color, molecular weight, electrophilicity and other material characteristics, effectively adjust its conjugate length and intramolecular charge transfer, and adjust the highest occupied orbital and The lowest vacant orbital energy level can meet the needs of organic electroluminescent devices, so that it can give the device more excellent performance when applied in organic electroluminescent devices.
  • the present invention also provides an organic electroluminescent device, including a laminated light-transmitting substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode
  • the light-emitting layer contains the organic small molecule light-emitting material described above.
  • the small organic light-emitting material serves as a light-emitting guest material in the light-emitting layer.
  • the light-emitting layer includes one or more of the organic small molecule light-emitting materials having different structural formulas.
  • the light-emitting layer may be prepared by thermal evaporation, spin coating, brush coating, spray coating, dip coating, roll coating, printing, or inkjet printing.
  • the organic small molecule light emitting material used in the light emitting layer couples the donor unit 10H-spiro [cridine-9,2'-adamantane] to the acceptor unit through the Hartwig-Buchwald coupling reaction Obtained, with high external quantum efficiency and excellent light-emitting performance.
  • the solvent was removed by pressure distillation, 100 mL of glacial acetic acid was added, N 2 was passed for 20 minutes, 5 mL of concentrated hydrochloric acid was added, and the mixture was heated to reflux and stirred for 24 hours.
  • the mixture was poured into 500 mL of water, and the product was extracted with dichloromethane.
  • the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed after separation, and it was separated and purified with a silica gel chromatography column to obtain a white solid (1.5 g, 62%).
  • Example 5 By analyzing and comparing the above Example 5 and Example 6, it is found that the reaction method using glacial acetic acid, concentrated hydrochloric acid and heating can effectively promote the progress of the reaction.
  • Example 7 Compared with Example 7, the difference is that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine is replaced with an equimolar amount of 2- (4-bromo Phenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, other raw materials and steps are the same as in Example 7, and the final yield of the solid product is 75%.
  • Product molecular formula C45H40N4; molecular weight: 636.33; elemental analysis results: C, 84.87; H, 6.33; N, 8.80.
  • Example 7 Compared with Example 7, the difference is that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine is replaced with an equimolar amount of 2- (4-bromo Phenyl) -4,6-bis (2-methylphenyl) -1,3,5-triazine, the other raw materials and steps are the same as in Example 7, and the final yield of the solid product is 75%.
  • Product molecular formula C45H40N4; molecular weight: 636.32; elemental analysis results: C, 84.87; H, 6.30; N, 8.83.
  • Example 7 Compared with Example 7, the difference is that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine is replaced with an equimolar amount of 2- (4-bromo Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, other raw materials and steps are the same as in Example 7, and the final yield of the solid product is 65% .
  • Product molecular formula C47H44N4; molecular weight: 664.36; elemental analysis results: C, 84.90; H, 6.67; N, 8.43.
  • the thermal stability of the organic small molecule light-emitting material 1 based on the 10H-spiro [acridine-9,2'-adamantane] donor unit prepared in Example 7 was tested to clarify the molecular stability of the material And the feasibility of applying vacuum evaporation to organic light-emitting devices.
  • the specific implementation steps are as follows: Thermogravimetric analysis (TGA) is measured on Netzsch TG 209, the heating rate is 10 °C min -1 under nitrogen protection, the heating end point is greater than 600 °C, as shown in Figure 1, after testing, molecule 1
  • the thermal decomposition temperature is 420 °C. It has a very high decomposition temperature, it is easy to obtain high-purity photoelectric materials by gradient sublimation, and it is suitable for electroluminescent devices.
  • This example prepares an organic electroluminescent molecule using the organic small molecule luminescent material molecule 1 prepared in Example 7 based on the 10H-spiro [acridine-9,2'-adamantane] donor unit for the luminescent layer guest material Light emitting device, the specific stack structure is as follows:
  • indium tin oxide is the anode
  • TAPC is the hole transport layer
  • TmPyPB is the electron transport layer
  • lithium fluoride is the electron injection layer
  • aluminum is the cathode
  • molecule 1: DPEPO is the light emitting layer.
  • the preparation method is as follows: the transparent conductive indium tin oxide glass substrate is sequentially cleaned with acetone, micron-level semiconductor special detergent, deionized water, and isopropyl alcohol for 15 minutes to remove the dirt on the substrate surface. Then put it in a thermostat at 80 degrees Celsius to dry it for use. The dried indium tin oxide substrate is treated with an oxygen plasma ignition device for 4 minutes to further remove organic contaminants attached to the surface.
  • TAPC, light-emitting layer material, TmPyPB, lithium fluoride, and aluminum are thermally deposited on the light-emitting layer by vacuum thermal evaporation to obtain the organic electroluminescent device of this embodiment.
  • a 10- (4- (4,6-phenyl-1,3,5-triazine-2-yl) phenyl) -9,9-dimethyl-9,10- Dihydroacridine (abbreviated as: DMAc-TRZ) (structure shown below) is used as an organic electroluminescent device for the guest material of the light emitting layer.
  • the specific stacked structure of the organic electroluminescent device is as follows: glass substrate / indium tin oxide (125 nanometers) / TAPC (40 nanometers) / 20wt% or 30wt% Lithium (1 nanometer) / Aluminum (100 nanometers).
  • Indium tin oxide is the anode
  • TAPC is the hole transport layer
  • TmPyPB is the electron transport layer
  • lithium fluoride is the electron injection layer
  • aluminum is the cathode
  • DMAc-TRZ: DPEPO is the light emitting layer.
  • the preparation method of the organic electroluminescent device in this implementation is the same as the method in Example 12.
  • the brightness and radiant energy density of electromechanical light-emitting devices prepared according to Example 12 and Comparative Example 13 at different voltages were tested with a CS-200 spectroradiometer and PR745 spectroscopic instrument. According to the current density and brightness of the organic electroluminescent device at different voltages, the current efficiency and external quantum efficiency (EQE) of the organic electroluminescent device are obtained.
  • EQE external quantum efficiency
  • Example 12 By comparing and analyzing Example 12 and Example 13, the following conclusions can be obtained: under the same device conditions, compared with the molecular DMAc-TRZ, molecule 1 obtains more excellent external quantum efficiency and bluer electroluminescence Spectrum, the reason may be: by replacing the two CH 3 hydrogen atoms of the acridine group, the super conjugate electron donation effect in molecule 1 is effectively reduced.
  • the 10H-spiro [cridine-9,2'- The molecule composed of the adamantane] donor unit has a very rigid molecular structure, which effectively suppresses the relaxation process of the molecular configuration of the molecule under the excited state condition, and reduces the Stokes shift of molecule 1.
  • the two reasons above result in a bluer electroluminescence spectrum.
  • the rigid structure suppresses the non-radiative decay process of the molecule, improves the molecular photoluminescence quantum yield, and thus improves the device based on molecule 1 effectiveness.
  • the organic small molecule light-emitting material of the present invention has a role as a doping guest material in the light-emitting layer. Since blue light-emitting materials are very important for full-color display and white light photos, it is of great significance to prepare high-efficiency blue light materials with application potential.
  • the organic small molecule luminescent material of the present invention consists of a novel acridine donor unit 10H-spiro [cridine-9,2'-adamantane] based on a non-aromatic rigid structure adamantane, and
  • the acceptor unit is coupled, its structure is single, the molecular weight is determined, it is easy to purify, and the reproducibility of multiple synthesis is good. It has a low sublimation temperature and a high decomposition temperature, and the film morphology is stable.
  • Pyridin-9,2'-adamantane has a very rigid structure, a non-aromatic rigid structure adamantane as part of the donor structure, this small organic light-emitting material has a very high photoluminescence quantum yield in the state of thin film , which can effectively solve the problem of low efficiency of excited molecules due to configuration relaxation resulting in severe non-radiative attenuation when applied in organic electroluminescent devices, and can be changed by 10H-spiro [cridine-9,2 '-Adamantane]
  • the type of acceptor unit connected can adjust the material's luminous color, molecular weight, electrophilicity and other material properties, effectively control its conjugation length and intramolecular charge transfer, and adjust the highest occupied orbit and the lowest vacancy Orbital energy level to meet the needs of organic electroluminescent devices, so that when applied in organic electroluminescent devices can give the device more excellent performance.
  • the light-emitting layer uses the above-

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Abstract

公开了一种有机小分子发光材料及有机电致发光器件。所述有机小分子发光材料由一种新型吖啶给体单元10H-螺[吖啶-9,2'-金刚烷]与受体单元偶联得到，其结构单一，分子量确定，便于提纯，多次合成再现性好，具有较低的升华温度和较高的分解温度,薄膜形态稳定，并由于非芳香性的刚性结构金刚烷作为给体部分结构，该有机小分子发光材料在薄膜状态下具有非常高的光致发光量子产率，应用于有机电致发光器件中时，能有效地解决激发态分子由于构型弛豫导致严重非辐射衰减而使器件效率低下的问题。

Description

有机小分子发光材料及有机电致发光器件 技术领域
本发明涉及有机电致发光领域，特别涉及一种有机小分子发光材料及采用该有机小分子发光材料的有机电致发光器件。
背景技术
有机电致发光(OLED)器件是一种自发光器件，具有电压低，视角宽、响应速度快、温度适应性好等优势，是新一代的显示技术，目前少数某些厂家已量产出OLED面板，而更多一些公司也进入研发和量产阶段。
有机电致发光器件的原理在于，在电场作用下，空穴和电子分别从阳极和阴极注入，分别通过空穴注入层、空穴传输层和电子注入层、电子传输层，在发光层复合形成激子，激子辐射衰减发光。
有机电致发光材料作为有机电致发光器件的核心组成部分，对器件的使用性能具有很大的影响。其中，高量子效率的荧光特性、良好的半导体特性、高质量的成膜特性、良好的化学稳定性和热稳定性、良好的加工性能等是其主要的性能要素。根据分子结构特性以发光波长范围来分类，包括有机小分子发光材料、有机配合物发光材料以及有机聚合物发光材料。
为了改善有机光电器件的效率和寿命，有机配合物发光材料基本为重金属配合物，生产成本较高，不利于大规模生产，且在高电流密度下有机配合物发光材料存在严重的效率滚降现象，此外，有机配合物发光材料的稳定性也并不好，而有机小分子发光材料相比于聚合物材料而言，由于制备步骤少，结构稳定，方便纯化，因而可以获得更高的器件效率，以至于更有可能得到商业化应用。目前，利用有机小分子发光材料制备的柔性OLED器件，因其具有无可比拟的优点而得到了极大的关注，并且取得了巨大的进展。
至今有机发光二极管已经取得了长足的进展，科学家们提出了各种各样的理论来解释发光的机理。但是至今为止，结构简单、且兼具良好性能、满足商业化需求的有机小分子光电材料依旧十分有限，开发新的有机光电材料依然具有举足轻重的意义。
发明内容
本发明的目的在于提供一种有机小分子发光材料，在薄膜状态下具有 非常高的光致发光量子产率，为良好的电子空穴双传输性质的发光客体材料。
本发明的另一目的在于提供有机电致发光器件，发光层采用上述有机小分子发光材料，具有较高的外量子效率及优良的发光性能。
为实现上述目的，本发明提供一种有机小分子发光材料，以10H-螺[吖啶-9,2’-金刚烷]为给体单元，是通过将受体单元与给体单元偶联得到的发光材料；
10H-螺[吖啶-9,2’-金刚烷]的化学结构式为
Figure PCTCN2018124982-appb-000001
所述有机小分子发光材料的化学结构通式如下式(I)所示，
Figure PCTCN2018124982-appb-000002
式(I)中，Ar为具有缺电子性的芳香性取代基。
所述的有机小分子发光材料以2,4,6-三苯基三嗪、2,4,6-三苯基吡嗪、1,3-苯二甲腈、3,5-苯二甲腈、二苯膦酰基、二苯硫砜基、吩噁嗪-10,10’-二氧化物、三(2,6-二甲苯基)硼、噻蒽-5,5,10,10-四氧化物、9-噻吨酮或9-占吨酮为受体单元。
式(I)中，Ar为
Figure PCTCN2018124982-appb-000003
Figure PCTCN2018124982-appb-000004
所述有机小分子发光材料的化学结构式为
Figure PCTCN2018124982-appb-000005
Figure PCTCN2018124982-appb-000006
所述有机小分子发光材料以给体单元10H-螺[吖啶-9,2’-金刚烷]与受体单元为原料，通过Hartwig-Buchwald偶合反应制备得到。
10H-螺[吖啶-9,2’-金刚烷]是以苯胺、邻溴碘苯和金刚烷酮为起始原料，依次通过Hartwig-Buchwald偶合反应及(Boc) 2O加保护反应制备得到。
本发明还提供一种有机电致发光器件，包括层叠设置的透光基板、阳极层、空穴注入层、空穴传输层、发光层、电子传输层及阴极层；
所述发光层包含如上所述的有机小分子发光材料。
所述有机小分子发光材料在所述发光层中作为发光客体材料。
所述发光层包含一种或多种具有不同结构式的所述有机小分子发光材料。
所述发光层通过热蒸镀、旋涂、刷涂、喷涂、浸涂、辊涂、印刷或喷墨打印的方式制备形成。
本发明的有益效果：本发明有机小分子发光材料，由一种新型的基于非芳香性的刚性结构金刚烷的吖啶给体单元10H-螺[吖啶-9,2’-金刚烷]，与受体单元偶联得到，其结构单一，分子量确定，便于提纯，多次合成再现性好，具有较低的升华温度和较高的分解温度,薄膜形态稳定，由于给体单元10H-螺[吖啶-9,2’-金刚烷]具有非常刚性的结构，非芳香性的刚性结构金刚烷作为给体部分结构，该有机小分子发光材料在薄膜状态下具有非常高的光致发光量子产率，应用于有机电致发光器件中时能有效地解决激发态分子由于构型弛豫导致严重非辐射衰减而使器件效率低下的问题，并可通过改变与10H-螺[吖啶-9,2’-金刚烷]连接的受体单元的种类，可以调节材料的发光颜色、分子量、亲电性等材料特性，有效地调控其共轭长度和分子内电荷转移，并调节最高占据轨道和最低空置轨道能级来满足有机电致发光器件的需要，从而在有机电致发光器件中应用时可赋予器件更优异的性能。本发明的机电致发光器件，发光层采用上述有机小分子发光材料，可 以有效提高有机电致发光器件的外量子效率，具有优异的器件性能。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为实施例7中所制备得到的分子1的热重分析图；
图2为实施例7、8、9和10中所制备得到的分子1、2、3和4在甲苯溶液中吸收光谱图；
图3为实施例7、8、9和10中所制备得到的分子1、2、3和4在甲苯溶液中荧光发射光谱图；
图4为以实施例7中所制备得到的分子1作为为发光层客体材料的有机电致发光器件的电流密度-电压-亮度曲线图；
图5为以实施例7中所制备得到的分子1作为发光层客体材料的有机电致发光器件的电流效率-亮度关系曲线图；
图6为以实施例7中所制备得到的分子1作为发光层客体材料的有机电致发光器件的外量子效率-亮度关系曲线图；
图7为以实施例7所制备得到的分子1作为发光层客体材料的有机电致发光器件的发光光谱；
图8为以化合物DMAc-TRZ作为发光层客体材料的有机电致发光器件的电流密度-电压-亮度曲线图；
图9为以化合物DMAc-TRZ作为发光层客体材料的有机电致发光器件的电流效率-亮度关系曲线图；
图10为以化合物DMAc-TRZ作为发光层客体材料的有机电致发光器件的外量子效率-亮度关系曲线图；
图11为以化合物DMAc-TRZ作为发光层客体材料的有机电致发光器件的发光光谱。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
本发明提供一种有机小分子发光材料，采用一种新型的基于非芳香性的刚性结构金刚烷的吖啶给体单元10H-螺[吖啶-9,2’-金刚烷]，通过Hartwig-Buchwald偶合反应将给体单元10H-螺[吖啶-9,2’-金刚烷]与受体单元偶联得到的发光材料。
其中，10H-螺[吖啶-9,2’-金刚烷]是依次通过Hartwig-Buchwald反应、(Boc) 2O加保护反应、低温反应、常温或高温闭环反应等一系列的简单反应获得，其化学结构式为
Figure PCTCN2018124982-appb-000007
由于金刚烷固有的刚性结构可以提高分子整体的刚性，从而可有效地降低其所组成的有机小分子发光材料分子在激发态下因几何构型变形导致的能量损失，因此利用该给体单元10H-螺[吖啶-9,2’-金刚烷]获得的有机小分子发光材料在薄膜状态下具有非常高的光致发光量子产率，进而有助于提高器件的效率及稳定性。
所述有机小分子发光材料的化学结构通式如下式(I)所示，
Figure PCTCN2018124982-appb-000008
式(I)中，Ar为具有缺电子性的芳香性取代基。
具体地，所述有机小分子发光材料是以2,4,6-三苯基三嗪、2,4,6-三苯基吡嗪、1,3-苯二甲腈、3,5-苯二甲腈、二苯膦酰基、二苯硫砜基、吩噁嗪-10,10’-二氧化物、三(2,6-二甲苯基)硼、噻蒽-5,5,10,10-四氧化物、9-噻吨酮或9-占吨酮等常用缺电子性芳香化合物及其衍生物为受体单元。
示例性地，式(1)中，Ar可以为
Figure PCTCN2018124982-appb-000009
Figure PCTCN2018124982-appb-000010
则所述的有机小分子发光材料的化学结构式相应为
Figure PCTCN2018124982-appb-000011
具体地，10H-螺[吖啶-9,2’-金刚烷]是以苯胺、邻溴碘苯和金刚烷酮为起始原料，依次通过Hartwig-Buchwald偶合反应及(Boc) 2O加保护反应等一系列简单反应制备得到。
本发明的有机小分子发光材料，由一种新型的基于非芳香性的刚性结构金刚烷的吖啶给体单元10H-螺[吖啶-9,2’-金刚烷]，与受体单元偶联得到，其结构单一，分子量确定，便于提纯，多次合成再现性好，具有较低的升华温度和较高的分解温度,薄膜形态稳定，由于给体单元10H-螺[吖啶-9,2’-金刚烷]具有非常刚性的结构，非芳香性的刚性结构金刚烷作为给体部分结构，利用该给体单元获得的有机小分子发光材料在薄膜状态下具有非常高的光致发光量子产率，应用于有机电致发光器件中时能有效地解决激发态分子由于构型弛豫导致严重非辐射衰减而使器件效率低下的问题，并可通过改变与10H-螺[吖啶-9,2’-金刚烷]连接的受体单元的种类，可以调节材料的发光颜色、分子量、亲电性等材料特性，有效地调控其共轭长度和分子内电荷转移，并调节最高占据轨道和最低空置轨道能级来满足有机电致发光器件的需要，从而在有机电致发光器件中应用时可赋予器件更优异的性能。
基于上述的有机小分子发光材料，本发明还提供一种有机电致发光器 件，包括层叠设置的透光基板、阳极层、空穴注入层、空穴传输层、发光层、电子传输层及阴极层；所述发光层包含以上所述的有机小分子发光材料。
具体地，所述有机小分子发光材料在所述发光层中作为发光客体材料。
具体地，所述发光层包含一种或多种具有不同结构式的所述有机小分子发光材料。
具体地，所述发光层可以通过热蒸镀、旋涂、刷涂、喷涂、浸涂、辊涂、印刷或喷墨打印的方式制备形成。
本发明的有机电致发光器件，发光层所采用的有机小分子发光材料通过Hartwig-Buchwald偶合反应将给体单元10H-螺[吖啶-9,2’-金刚烷]与受体单元偶联得到，具有较高的外量子效率及优良的发光性能。
以下通过具体实施例对本发明进行详细说明，但本发明并非局限在实施例范围。
实施例1
2-溴-N-苯基苯胺的合成方法1，化学反应式如下：
Figure PCTCN2018124982-appb-000012
在250mL的三口烧瓶中，在室温条件下依次加入苯胺(0.2mol，18.6g)，邻溴碘苯(0.2mol，56.58g)、醋酸钯(0.6mmol，134.4mg)、叔丁醇钠(0.4mol)依次加入烧瓶中，然后加入150mL的甲苯，通N 2 20分钟，然后加入特丁基膦(1.2mmol，1.2ml)，继续通N 2 20分钟，加热至回流并搅拌12小时。降温至室温，抽滤除去叔丁醇钠，加压蒸馏除去溶剂，用硅胶色谱柱分离提纯得到无色油状液体(27.8g，产率56％)。
实施例2
2-溴-N-苯基苯胺的合成方法2，化学反应式如下：
Figure PCTCN2018124982-appb-000013
在250mL的三口烧瓶中，在室温条件下依次加入苯胺(0.2mol，18.6g)，邻溴碘苯(0.2mol，56.58g)、醋酸钯(0.6mmol，134.4mg)、叔丁醇钠(0.4mol)依次加入烧瓶中，邻双(2-苯基)二(二苯基膦)(0.6mmol，340mg)，然后加入150mL的甲苯，通N 2 20分钟，加热至回流并搅拌12小时。降温至室温，抽滤除去叔丁醇钠，加压蒸馏除去溶剂，用硅胶色谱柱分离提纯得到无色 油状液体(44.2g，产率89％)。
将以上实施例1和实施例2进行对比后可以发现，通过将催化剂配体由特丁基膦改变为邻双(2-苯基)二(二苯基膦)，2-溴-N-苯基苯胺产率由56％提高到了89％。
实施例3
(4-溴苯基)-苯基-氨基甲酸叔丁基酯的制备方法1，化学反应式如下：
Figure PCTCN2018124982-appb-000014
在500毫升单口烧瓶中，在室温下将二碳酸二叔丁酯(BOC)(0.2mol，43.6g)加入到400毫升的四氢呋喃中，然后再加入对N-(二溴苯)苯胺(0.1mol，24.8g)，加热至回流并搅拌24小时。然后将混合液倒入1L水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到无色油状液体(32.0g，产率92％)。
实施例4
(4-溴苯基)-苯基-氨基甲酸叔丁基酯的制备方法2：
在500毫升单口烧瓶中，在室温下将二碳酸二叔丁酯(BOC)(0.2mol，43.6g)加入到400毫升的四氢呋喃中，然后再加入对N-(二溴苯)苯胺(0.1mol，24.8g)，通N 2 20分钟并加热至回流并搅拌24小时。然后将混合液倒入1L水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到无色油状液体(33.0g，产率95％)。
通过实施例3和4分析，发现通N 2与不通N 2对反应产率影响不大，说明该反应对氧气不敏感。
实施例5
10H-螺[吖啶-9,2'-金刚烷]的制备方法1，化学反应式如下：
Figure PCTCN2018124982-appb-000015
在200毫升三口烧瓶中，将实施例3或实施例4中制备得到的(4-溴苯基)-苯基-氨基甲酸叔丁基酯(8mmol，2.8g)加入到60毫升的无水四氢呋喃中，然后降温至零下80℃，再缓慢滴入1.6M的正丁基锂(9mmol，5.2mL)。在氩气气氛下继续搅拌2小时。加入金刚烷酮(8.1mmol，1.2g)于25毫升四氢呋喃的溶液，继续搅拌2小时然后缓慢升温至室温。然后加入15毫升稀盐酸(1M)，再继续搅拌12小时后，将混合液倒入500毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体(0.5g，20.7％)。
实施例6
10H-螺[吖啶-9,2'-金刚烷]的制备方法2，化学反应式如下：
Figure PCTCN2018124982-appb-000016
在200毫升三口烧瓶中，将实施例3或实施例4中制备得到的(4-溴苯基)-苯基-氨基甲酸叔丁基酯(8mmol，2.8g)加入到60毫升的无水四氢呋喃中，然后降温至零下80℃，再缓慢滴入1.6M的正丁基锂(9mmol，5.2mL)。在氩气气氛下继续搅拌2小时。加入金刚烷酮(8.1mmol，1.2g)于25毫升四氢呋喃的溶液，继续搅拌2小时然后缓慢升温至室温。加压蒸馏除去溶剂，加入100mL冰乙酸，通N 2 20分钟，加入5毫升浓盐酸，并加热至回流并搅拌24小时后，将混合液倒入500毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到白色固体(1.5g，62％)。
通过分析对比上述实施例5和实施例6，发现采用冰乙酸、浓盐酸并加热的反应方法可以有效地促进反应的进行。
实施例7
具有结构式1的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料的制备，化学反应式如下：
Figure PCTCN2018124982-appb-000017
在氩气气氛下向反应瓶中加入10H-螺[吖啶-9,2'-金刚烷](2.4mmol，0.72g)和2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪(2.8mmol，1.09g)，50毫升甲苯作为溶剂，醋酸钯60毫克，三叔丁基磷(0.5mmol，0.11g)和0.48克叔丁醇钠。加热回流下搅拌反应24小时，冷却后，将混合液倒入200毫升水中，并用二氯甲烷萃取产物。无水硫酸镁干燥有机相，分离后去除溶剂，用硅胶色谱柱分离提纯得到淡青色固体。经过干燥后于真空条件下升华得到高纯度产物(0.72g，49％)。分子式为：C43H36N4；分子量为：608.29；元素分析结果为：C，84.84；H，5.96；N，9.20。
实施例8
具有结构式2的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料的制备，化学反应式如下：
Figure PCTCN2018124982-appb-000018
与实施例7相比，不同之处在于将2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪换成等摩尔量的2-(4-溴苯基)-4,6-二(4-甲基苯基)-1,3,5-三嗪，其他原料和步骤均与实施例7相同，最终得到固体产物的产率75％。产物分子式：C45H40N4；分子量：636.33；元素分析结果为：C，84.87；H，6.33；N，8.80。
实施例9
具有结构式3的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料的制备，化学反应式如下：
Figure PCTCN2018124982-appb-000019
与实施例7相比，不同之处在于将2-(4-溴苯基)-4,6-二苯基-1,3,5-三 嗪换成等摩尔量的2-(4-溴苯基)-4,6-二(2-甲基苯基)-1,3,5-三嗪，其他原料和步骤均与实施例7相同，最终得到固体产物的产率75％。产物分子式：C45H40N4；分子量：636.32；元素分析结果为：C，84.87；H，6.30；N，8.83。
实施例10
具有结构式4的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料的制备，化学反应式如下：
Figure PCTCN2018124982-appb-000020
与实施例7相比，不同之处在于将2-(4-溴苯基)-4,6-二苯基-1,3,5-三嗪换成等摩尔量的2-(4-溴苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪，其他原料和步骤均与实施例7相同，最终得到固体产物的产率65％。产物分子式：C47H44N4；分子量为：664.36；元素分析结果为：C，84.90；H，6.67；N，8.43。
实施例11
本实施例测试了实施例7制备得到的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料1的热稳定性，以明确该材料的分子稳定性以及按真空蒸镀方式应用于有机发光器件中的可行性。具体实施步骤如下：热重分析(TGA)是在Netzsch TG 209上测得，在氮气保护下加热速度为10℃min -1，加热终点大于600℃，如图1所示，经过测试，分子1的热分解温度为420℃。具有很高的分解温度，容易通过梯度升华的方式获得高纯度的光电材料使用，并且适用于电致发光器件中。
实施例12
制备有机电致发光器件
本实施例制备一种将实施例7制备得到的基于10H-螺[吖啶-9,2’-金刚烷]给体单元的有机小分子发光材料分子1用于发光层客体材料的有机电致发光器件，具体层叠结构如下：
玻璃基板/氧化铟锡(125纳米)/TAPC(40纳米)/20wt％或30wt％分子1:DPEPO(30纳米)/TmPyPB(50纳米)/氟化锂(1纳米)/铝(100纳米)。其中，氧化铟锡为阳极，TAPC作为空穴传输层，TmPyPB作为电子传输层，氟化锂作为电子注入层，铝作为阴极，分子1:DPEPO为发光层。
制备方法如下：将透明导电的氧化铟锡玻璃基板依次用丙酮、微米级半导体专用洗涤剂、去离子水、异丙醇超声清理15分钟，以除去衬底表面的污垢。随后放入恒温箱中80摄氏度烘干待用。烘干后的氧化铟锡基板用氧等离子体起辉设备处理4分钟，进一步除去表面附着的有机污染物。将TAPC、发光层材料、TmPyPB、氟化锂和铝以真空热蒸镀的方式热沉积在发光层上，得到本实施例的有机电致发光器件。
对比实施例13
制备有机电致发光器件
本实施例制备了一种将10-(4-(4,6-苯基-1,3,5-三嗪-2-yl)苯基)-9,9-二甲基-9,10-二氢吖啶(简写为：DMAc-TRZ)(结构如下所示)用于发光层客体材料的有机电致发光器件。
Figure PCTCN2018124982-appb-000021
有机电致发光器件具体层叠结构如下：玻璃基板/氧化铟锡(125纳米)/TAPC(40纳米)/20wt％或30wt％DMAc-TRZ:DPEPO(40纳米)/TmPyPB(50纳米)/氟化锂(1纳米)/铝(100纳米)。氧化铟锡为阳极，TAPC作为空穴传输层，TmPyPB作为电子传输层，氟化锂作为电子注入层，铝作为阴极，DMAc-TRZ:DPEPO为发光层。
本实施中有机电致发光器件制备方法如实施例12方法一致。
有机光电装置的性能评价
用Keithley 2400数字纳伏测试根据实施例12以及对比实施例13制备的有机电致发光器件在不同的电压下的电流，以奇偶用电流除以面积得到有机电致发光器件在不同电压下的电流密度。
用CS-200分光辐射亮度计和PR745光谱仪器测试根据实施例12以及对比实施例13制备的机电致发光器件在不同电压下的亮度和辐射能量密度。根据有机电致发光器件在不同电压下的电流密度和亮度，得到有机电致发光器件的电流效率和外部量子效率(EQE)。
实施例12的有机电致发光器件的电流密度-电压-亮度关系曲线图、电流效率-亮度关系曲线图、外量子效率-亮度关系曲线图和发光光谱曲线分别如图4、图5、图6和图7所示。
实施例13的有机电致发光器件的电流密度-电压-亮度关系曲线图、电流效率-亮度关系曲线图、外量子效率-亮度关系曲线图和发光光谱曲线分别 如图8、图9、图10和图11所示。
实施例12和实施例13的有机电致发光器件的启动电压、最大电流效率、最大外量子效率、CIE坐标等数据汇总如下表1中示出。
表1
Figure PCTCN2018124982-appb-000022
通过对实施例12和实施例13进行对比分析可获得如下结论：在同样的器件条件下，与分子DMAc-TRZ相比，分子1获得了更为优异的外量子效率和更蓝的电致发光光谱，原因可能是：通过取代吖啶基团两个CH 3的氢原子，有效地降低了分子1中的超共轭给电子作用，此外，由10H-螺[吖啶-9,2’-金刚烷]给体单元组成的分子具有非常刚性的分子结构，有效地抑制了分子在激发态条件下的分子构型的弛豫过程，降低了分子1的斯托克斯位移。由上述两个原因导致了更蓝的电致发光光谱。与DMAc-TRZ相比，获得了更高的外量子效率，原因可能是刚性的结构抑制了分子的非辐射衰减过程，提高了分子光致发光量子产率，从而提高了基于分子1的器件的效率。这表明了本发明的有机小分子发光材料具有作为发光层中掺杂客体材料的作用。由于蓝色发光材料对于全光色显示和白光照片具有非常重要的意义，因此制备具有应用潜力的高效蓝光材料意义重大。
实施例12和实施例13中所述的TAPC、mCP、DPEPO和TmPyPB的分子结构式分别如下所示：
Figure PCTCN2018124982-appb-000023
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变，修饰，替代，组合，简化均应为等效的置换方式，都包含在本发明的保护范围之内。
综上所述，本发明有机小分子发光材料，由一种新型的基于非芳香性的刚性结构金刚烷的吖啶给体单元10H-螺[吖啶-9,2’-金刚烷]，与受体单元偶联得到，其结构单一，分子量确定，便于提纯，多次合成再现性好，具有较低的升华温度和较高的分解温度,薄膜形态稳定，由于给体单元10H-螺[吖啶-9,2’-金刚烷]具有非常刚性的结构，非芳香性的刚性结构金刚烷作为给体部分结构，该有机小分子发光材料在薄膜状态下具有非常高的光致发光量子产率，应用于有机电致发光器件中时能有效地解决激发态分子由于构型弛豫导致严重非辐射衰减而使器件效率低下的问题，并可通过改变与10H-螺[吖啶-9,2’-金刚烷]连接的受体单元的种类，可以调节材料的发光颜色、分子量、亲电性等材料特性，有效地调控其共轭长度和分子内电荷转移，并调节最高占据轨道和最低空置轨道能级来满足有机电致发光器件的需要，从而在有机电致发光器件中应用时可赋予器件更优异的性能。本发明的机电致发光器件，发光层采用上述有机小分子发光材料，可以有效提高有机电致发光器件的外量子效率，具有优异的器件性能。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (15)

  1. 一种有机小分子发光材料，以10H-螺[吖啶-9,2’-金刚烷]为给体单元，是通过将受体单元与给体单元偶联得到的发光材料；
    10H-螺[吖啶-9,2’-金刚烷]的化学结构式为
    Figure PCTCN2018124982-appb-100001
    所述有机小分子发光材料的化学结构通式如下式(I)所示，
    Figure PCTCN2018124982-appb-100002
    式(I)中，Ar为具有缺电子性的芳香性取代基。
  2. 如权利要求1所述的有机小分子发光材料，其中，以2,4,6-三苯基三嗪、2,4,6-三苯基吡嗪、1,3-苯二甲腈、3,5-苯二甲腈、二苯膦酰基、二苯硫砜基、吩噁嗪-10,10’-二氧化物、三(2,6-二甲苯基)硼、噻蒽-5,5,10,10-四氧化物、9-噻吨酮或9-占吨酮为受体单元。
  3. 如权利要求2所述的有机小分子发光材料，其中，式(1)中，Ar为
    Figure PCTCN2018124982-appb-100003
  4. 如权利要求2所述的有机小分子发光材料，其化学结构式为
    Figure PCTCN2018124982-appb-100004
    Figure PCTCN2018124982-appb-100005
  5. 如权利要求1所述的有机小分子发光材料，是以给体单元10H-螺[吖啶-9,2’-金刚烷]与受体单元为原料，通过Hartwig-Buchwald偶合反应制备得到。
  6. 如权利要求1所述的有机小分子发光材料，其中，10H-螺[吖啶-9,2’-金刚烷]是以苯胺、邻溴碘苯和金刚烷酮为起始原料，依次通过Hartwig-Buchwald偶合反应及(Boc) 2O加保护反应制备得到。
  7. 一种有机电致发光器件，包括层叠设置的透光基板、阳极层、空穴注入层、空穴传输层、发光层、电子传输层及阴极层；所述发光层包含有机小分子发光材料，所述有机小分子发光材料以10H-螺[吖啶-9,2’-金刚烷]为给体单元，是通过将受体单元与给体单元偶联得到的发光材料；
    10H-螺[吖啶-9,2’-金刚烷]的化学结构式为
    Figure PCTCN2018124982-appb-100006
    所述有机小分子发光材料的化学结构通式如下式(I)所示，
    Figure PCTCN2018124982-appb-100007
    式(I)中，Ar为具有缺电子性的芳香性取代基。
  8. 如权利要求7所述的有机电致发光器件，其中，所述有机小分子发光材料在所述发光层中作为发光客体材料。
  9. 如权利要求7所述的有机电致发光器件，其中，所述发光层包含一种或多种具有不同结构式的所述有机小分子发光材料。
  10. 如权利要求7所述的有机电致发光器件，其中，所述发光层通过热蒸镀、旋涂、刷涂、喷涂、浸涂、辊涂、印刷或喷墨打印的方式制备形成。
  11. 如权利要求7所述的有机电致发光器件，其中，以2,4,6-三苯基三嗪、2,4,6-三苯基吡嗪、1,3-苯二甲腈、3,5-苯二甲腈、二苯膦酰基、二苯硫 砜基、吩噁嗪-10,10’-二氧化物、三(2,6-二甲苯基)硼、噻蒽-5,5,10,10-四氧化物、9-噻吨酮或9-占吨酮为受体单元。
  12. 如权利要求11所述的有机电致发光器件，其中，式(1)中，Ar为
    Figure PCTCN2018124982-appb-100008
  13. 如权利要求11所述的有机电致发光器件，其中，所述有机小分子发光材料的化学结构式为
    Figure PCTCN2018124982-appb-100009
    Figure PCTCN2018124982-appb-100010
  14. 如权利要求7所述的有机电致发光器件，其中，所述有机小分子发光材料是以给体单元10H-螺[吖啶-9,2’-金刚烷]与受体单元为原料，通过Hartwig-Buchwald偶合反应制备得到。
  15. 如权利要求7所述的有机电致发光器件，其中，10H-螺[吖啶-9,2’-金刚烷]是以苯胺、邻溴碘苯和金刚烷酮为起始原料，依次通过Hartwig-Buchwald偶合反应及(Boc) 2O加保护反应制备得到。
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