WO2018050107A1 - 一种有机发光材料及其在oled上的应用 - Google Patents

一种有机发光材料及其在oled上的应用 Download PDF

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WO2018050107A1
WO2018050107A1 PCT/CN2017/102008 CN2017102008W WO2018050107A1 WO 2018050107 A1 WO2018050107 A1 WO 2018050107A1 CN 2017102008 W CN2017102008 W CN 2017102008W WO 2018050107 A1 WO2018050107 A1 WO 2018050107A1
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group
thickness
compound
organic electroluminescent
substituted
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PCT/CN2017/102008
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French (fr)
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叶中华
李崇
张兆超
徐凯
张小庆
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江苏三月光电科技有限公司
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Publication of WO2018050107A1 publication Critical patent/WO2018050107A1/zh

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Definitions

  • the present invention relates to the field of semiconductor technology, and in particular to the synthesis of a fluorescent compound and the use as a dopant material for an luminescent layer on an organic light emitting diode.
  • OLED Organic Light Emission Diodes
  • OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television.
  • the luminous efficiency and service life of the OLED device need to be further improved.
  • the OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device.
  • As a current device when a voltage is applied to the electrodes of both ends of the OLED light-emitting device, and positive and negative charges are applied to the organic layer functional material film layer by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.
  • Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device.
  • it is not only necessary to innovate from the structure and fabrication process of OLED devices, but also to continuously research and innovate OLED photoelectric functional materials, and to create functional materials with higher performance OLEDs.
  • the OLED photoelectric functional materials applied to the OLED device can be divided into two categories, namely, a charge injection transmission material and a luminescent material, and further, the charge injection transmission material can be further divided into an electron injection transmission material and a hole injection transmission material.
  • the luminescent material can also be divided into a host luminescent material and a dopant material.
  • various organic functional materials are required to have good photoelectric characteristics. For example, as a charge transport material, it is required to have good carrier mobility, high glass transition temperature, etc., as a material of the light-emitting layer. The material is required to have good fluorescence quantum efficiency, material evaporation stability, appropriate HOMO/LUMO energy levels, and the like.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two layers or more, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer and the like, and also That is to say, the photoelectric functional material applied to the OLED device includes at least a hole injecting material, a hole transporting material, a luminescent material, an electron injecting material, etc., and the material type and the collocation form are rich and diverse.
  • the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different.
  • the Applicant has provided an organic electroluminescent compound and its use.
  • the OLED device prepared by using the compound of the present invention as a host material or a doping material of the light-emitting layer has good external quantum efficiency, material stability and color purity, and can meet the requirements of panel manufacturers.
  • the Applicant has provided an organic electroluminescent compound having a structure as shown in the general formula (1):
  • R 1 and R 2 are each independently represented by the formula (2), and R 1 and R 2 may be the same or different;
  • a is selected from One of them;
  • X 1 , X 2 and X 3 are each independently represented by an oxygen atom, a sulfur atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group.
  • X 4 and X 5 are each independently represented by an alkyl group having 1 to 6 carbon atoms or a phenyl group; or X 4 and X 5 are bonded to form an aryl ring having 10 to 16 carbon atoms;
  • a in R 1 is bonded to a C 1 -C 2 bond, a C 2 -C 3 bond, or a C 3 -C 4 bond to form a ring;
  • a in the R 2 is a C 5 -C 6 bond, a C 6 -C 7 bond, Or a C 7 -C 8 bond to form a ring;
  • R 3 and R 4 are each independently represented by an alkyl group having 1 to 6 carbon atoms or a phenyl group; or R 3 and R 4 are bonded to form an aryl ring having 10 to 16 carbon atoms;
  • R 5 is independently represented by one of a substituted or unsubstituted arylamino group, a substituted or unsubstituted nitrogen-containing heteroaryl group.
  • the compound is selected from any one of the general formulae (3) to (5):
  • R 5 and R 6 are independently represented by a substituted or unsubstituted arylamino group, a substituted or unsubstituted nitrogen-containing heteroaryl group.
  • R 5 and R 6 are each independently represented by the formula (6) or (7):
  • X 6 is an oxygen atom, a sulfur atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group.
  • X 6 is an oxygen atom, a sulfur atom, a C 1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group.
  • R 7 and R 8 are each independently represented by hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group or an arylamine group; however, at least one of them is represented by an arylamine group.
  • R 5 and R 6 are each independently represented by the formula (8):
  • R 9 and R 10 are each independently represented by an aryl group or a heteroaryl group.
  • R 7 , R 8 , R 9 and R 10 are each independently represented by substituted or unsubstituted phenyl, pyridyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triazine
  • phenyl pyridyl
  • biphenyl terphenyl
  • naphthyl anthryl
  • phenanthryl triazine
  • a group a pyrimidinyl group, a quinolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a 9,9-dimethylindenyl group, or a 9,9-diphenylfluorenyl group.
  • the Applicant also provides an organic electroluminescent device containing the organic electroluminescent compound, which is applied as an emissive material for an organic electroluminescent diode.
  • the organic electroluminescent device When the organic electroluminescent compound is used as a light-emitting layer doping material, the organic electroluminescent device has a compound represented by the following general formula (a) as a host material:
  • R 1 - R 4 and R 7 - R 10 are each independently represented by a hydrogen atom, a C 1 - C 10 alkyl group or a cycloalkyl group, a substituted or unsubstituted aryl group, or a heteroaryl group. ;
  • n are independently selected from 0-3 integers, but not equal to 0 at the same time;
  • R 5 and R 6 each independently represent a substituted or unsubstituted aryl or heteroaryl group.
  • the compound of the invention can be applied to the fabrication of OLED light-emitting devices, and good device performance can be obtained.
  • the compound is used as a separate light-emitting layer material of an OLED light-emitting device or a light-emitting layer doping material, the luminous efficiency and power of the device can be obtained. Both efficiency and external quantum efficiency are greatly improved; device color purity is significantly improved, and device lifetime is improved.
  • the compound of the invention has good application effects in OLED light-emitting devices and has good industrialization prospects.
  • the invention has a dibenzoheptene structure as a core and is modified by a skeleton core, and the molecules of the structure have a strong spatial stereoscopic effect, can effectively reduce the aggregation effect between molecules, and inhibit the crystallization degree of the material, and at the same time
  • the molecule has good thermal stability and high fluorescence quantum efficiency. Therefore, this kind of material is used in organic light-emitting diodes, which can effectively improve device efficiency and life.
  • Figure 1 is a schematic illustration of an OLED device made from a compound of the present invention.
  • a transparent substrate layer 2, an ITO anode layer, 3, a hole injection layer, 4, a hole transport layer, 5, Light-emitting layer, 6, electron transport layer, 7, electron injection layer, 8, cathode reflective electrode layer.
  • Elemental Analysis Structure (Molecular Formula C 53 H 38 N 2 O 2 ): Theory C, 86.62; H, 5.21.; N, 3.81; O, 4.35. Tests: C, 86.67; H, 5.16; N, 3.80; O, 4.37
  • Elemental analysis structure (molecular formula C 82 H 80 N 2 O): theoretical value C, 88.77; H, 7.27; N, 2.52; O, 1.44
  • Elemental analysis structure (Molecular Formula C 77 H 52 N 4 O 2 ): Theory C, 86.82; H, 4.92; N, 5.26; O, 3.00;
  • Elemental analysis structure (molecular formula C 66 H 46 N 2 O 2 ): Theory C, 88.17; H, 5.16; N, 3.12; O, 3.56.
  • Elemental analysis structure (molecular formula C 63 H 40 N 2 O 4 ): theoretical value C, 85.11; H, 4.54; N, 3.15; O, 7.20
  • the inventive compound can be used as a light-emitting layer doping material.
  • the thermal stability, the fluorescence quantum efficiency, and the cyclic voltammetry stability of the compound 14, the compound 108, and the conventional material MQAB of the present invention were measured, and the results are shown in Table 1.
  • the thermal weight loss temperature Td is the temperature at which the weight loss is 1% in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL/min; Tg Japan Shimadzu DSC-60 The measurement was carried out by a differential scanning analyzer with a nitrogen flow rate of 10 mL/min.
  • Fluorescence quantum efficiency was identified by Quantaurus-QY (C13534-11) from HAMAMATSU, Japan; cyclic voltammetric stability was identified by cyclic voltammetry to observe the redox characteristics of the material; test conditions: test sample dissolved in volume ratio A 2:1 mixed solvent of dichloromethane and acetonitrile at a concentration of 1 mg/mL, and the electrolyte is an organic solution of 0.1 M tetrabutylammonium tetrafluoroborate or tetrabutylammonium hexafluorophosphate.
  • the reference electrode is an Ag/Ag+ electrode
  • the counter electrode is a titanium plate
  • the working electrode is an ITO electrode, and the number of cycles is 20 times.
  • the compound of the invention has good redox stability, high thermal stability and fluorescence quantum efficiency, and can be used as a light-emitting layer doping material, thereby improving the efficiency of the OLED device and life.
  • Comparative Examples 1, 2 and Examples 13 to 27 The application effects of the materials synthesized by the present invention on OLED devices will be described in detail below by Comparative Examples 1, 2 and Examples 13 to 27.
  • the fabrication process of the device was completely the same, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept the same, except that Some adjustments were made to some of the materials used in the device, and Comparative Examples 1, 2 used some of the OLED materials of the present invention.
  • the transparent glass substrate 1 is made of a transparent material.
  • the ITO anode layer 2 (having a film thickness of 150 nm) was washed, that is, washed with alkali, washed with pure water, dried, and then subjected to ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO.
  • HAT-CN On the ITO anode layer 2 after the above washing, HAT-CN was deposited by a vacuum vapor deposition apparatus to a film thickness of 10 nm, and this organic material was used as the hole injection layer 3.
  • TCTA 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • the light emitting layer 5 of the OLED light emitting device is fabricated, and the structure thereof includes the material mCP used as the host material of the OLED light emitting layer 5, MQAB as a doping material, and the doping ratio is 4% by weight, and the light is emitted.
  • the film thickness was 25 nm.
  • the vacuum evaporation of the electron transport layer material is continued as TPBi.
  • the vacuum evaporation film thickness of this material was 35 nm, and this layer was the electron transport layer 6.
  • a lithium fluoride (LiF) layer having a film thickness of 1 nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 7.
  • an aluminum (Al) layer having a film thickness of 80 nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflective electrode layer 8.
  • the material structure of each layer is as follows:
  • the structure of the fabricated OLED light-emitting device device is shown in Table 2, and the test results are shown in Table 3.
  • the anode and the cathode are connected by a known driving circuit, and the luminous efficiency, the color of the light, and the lifetime of the device (LT95: luminance is attenuated to 95% of the initial luminance) are measured.
  • TO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (NpPhAn and MQAB are blended in a weight ratio of 100:4, thickness 25 nm / Electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (mCP and compound 04 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (mCP and compound 08 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 14 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 22 are blended in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 38 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 43 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 51 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 58 are blended in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 70 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 73 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (mCP and compound 109 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (mCP and compound 118 are blended in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (NpPhAn and compound 73 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / light-emitting layer 5 (NpPhAn and compound 109 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • ITO anode layer 2 / hole injection layer 3 (HAT-CN, thickness 10 nm) / hole transport layer 4 (TCTA, thickness 70 nm) / luminescent layer 5 (NpPhAn and compound 118 are mixed in a weight ratio of 100:4, thickness 25 nm) / electron transport layer 6 (TPBi, thickness 35 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode reflective electrode layer 8 (Al, thickness 80 nm).
  • Example 13 3.8 blue 2.7 Example 14 4.0 blue 3.2 Example 15 4.1 blue 2.9 Example 16 3.9 blue 3.3 Example 17 4.3 blue 3.4 Example 18 4.5 blue 3.2 Example 19 4.6 blue 3.1 Example 20 4.2 blue 3.6 Example 21 4.8 blue 2.7 Example 22 5.0 blue 3.0 Example 23 4.5 blue 3.2 Example 24 3.5 blue 2.9 Example 25 5.3 blue 3.0 Example 26 5.1 blue 3.3 Example 27 5.4 blue 3.3
  • Comparative Example 1 As the standard device.
  • the current efficiency of Comparative Example 1 is 3.0 cd/A (@10 mA/cm 2 ); the CIE color coordinate is (0.15, 0.15); the lifetime attenuation of LT95 at 1000 brightness is 2Hr.
  • the life test system is the OLED device life tester jointly researched by the owner of the invention and Shanghai University.
  • the compounds of the present invention are applicable to the fabrication of OLED light-emitting devices, and good device performance can be obtained.
  • the luminous efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is greatly improved.
  • the compound of the invention has good application effects in OLED light-emitting devices and has good industrialization prospects.

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Abstract

公开了一种有机发光材料及其在OLED上的应用，该种材料具有良好的荧光量子效率和电致发光效率，具有良好的热稳定性，因此该类材料可作为有机电致发光器件中发光层掺杂材料使用。

Description

一种有机发光材料及其在OLED上的应用 技术领域
本发明涉及半导体技术领域，尤其是涉及一种荧光化合物的合成，以及作为发光层掺杂材料在有机发光二极管上的应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品，也可以用于制作新型照明产品，有望替代现有的液晶显示和荧光灯照明，应用前景十分广泛。
当前，OLED显示技术已经在智能手机，平板电脑等领域获得应用，进一步还将向电视等大尺寸应用领域扩展。但是，和实际的产品应用要求相比，OLED器件的发光效率，使用寿命等性能还需要进一步提升。
OLED发光器件犹如三明治的结构，包括电极材料膜层，以及夹在不同电极膜层之间的有机功能材料，各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件，当对OLED发光器件的两端电极施加电压，并通过电场作用有机层功能材料膜层中正负电荷，正负电荷进一步在发光层中复合，即产生OLED电致发光。
对于OLED发光器件提高性能的研究包括：降低器件的驱动电压，提高器件的发光效率，提高器件的使用寿命等。为了实现OLED器件的性能的不断提升，不但需要从OLED器件结构和制作工艺的创新，更需要OLED光电功能材料不断研究和创新，创制出更高性能OLED的功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类，即电荷注入传输材料和发光材料，进一步，还可将电荷注入传输材料分为电子注入传输材料和空穴注入传输材料，还可以将发光材料分为主体发光材料和掺杂材料。为了制作高性能的OLED发光器件，要求各种有机功能材料具备良好的光电特性，譬如，作为电荷传输材料，要求具有良好的载流子迁移率，高玻璃化转化温度等，作为发光层的材料要求材料具有良好的荧光量子效率、材料蒸镀稳定性、适当的HOMO/LUMO能级等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件结构，则包括空穴注入层、空穴传输层、发光层、电子注入层等多种膜层，也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料，空穴传输材料，发光材料，电子注入材料等，材料类型和搭配形式具有丰富性和多样性的特点。另外，对于不同结构的OLED器件搭配而言，所使用的光电功能材料具有较强的选择性，相同的材料在不同结构器件中的性能表现，也可能完全迥异。
目前，荧光材料研究方面已经取得了长足的发展，能够满足产业化的需求；但是其效率、寿命方面依然存在不足，不易达到全彩RGB的要求。因此，针对当前OLED显示照明产业的实际需求而言，荧光材料的发展还远远不够，落后于面板制造企业的要求，作为材料企业开发更高性能的有机功能荧光材料显得尤为重要。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种有机电致发光化合物及其应用。本发明化合物作为发光层主体材料或者掺杂材料制作出的OLED器件具有良好的外量子效率、材料稳定性以及色纯度，能够满足面板制造企业的要求。
本发明的技术方案如下：
本申请人提供了一种有机电致发光化合物，所述化合物的结构如通式(1)所示：
Figure PCTCN2017102008-appb-000001
通式(1)中，R1、R2分别独立的由通式(2)表示，R1、R2可以相同也可以不同；
Figure PCTCN2017102008-appb-000002
Figure PCTCN2017102008-appb-000003
通式(2)中，a选自
Figure PCTCN2017102008-appb-000004
中的一种；
X1、X2、X3分别独立的表示为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
X4、X5分别独立的表示为碳原子数1-6的烷基、或苯基；或者X4、X5通过键结形成碳原子数为10-16的芳基环；
R1中的a与C1-C2键、C2-C3键、或C3-C4连接成环；R2中的a与C5-C6键、C6-C7键、或C7-C8键连接成环；
R3、R4分别独立的表示为碳原子数1-6的烷基、或苯基；或者R3、R4通过键结形成碳原子数为10-16的芳基环；
R5独立地表示为取代或者未取代芳胺基、取代或者未取代的含氮杂芳基中的一种。
优选的，所述化合物选自通式通式(3)-(5)的任一种：
Figure PCTCN2017102008-appb-000005
其中R5、R6独立地表示为取代或未取代芳胺基、取代或未取代的含氮杂芳基。
优选的，所述R5、R6分别独立的采用通式(6)或(7)表示：
Figure PCTCN2017102008-appb-000006
通式(6)、(7)中，X6为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
R7、R8分别独立的表示为氢、碳原子数1-6的烷基、芳基、芳胺基；但至少有一个表示为芳胺基。
优选的，所述R5、R6分别独立的采用通式(8)表示：
Figure PCTCN2017102008-appb-000007
其中，R9、R10分别独立的表示为芳基、或杂芳基。
优选的，R7、R8、R9、R10分别独立的表示为取代或未取代的苯基、吡啶基、二联苯基、三联苯基、萘基、蒽基、菲基、三嗪基、嘧啶基、喹啉基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、或9,9-二苯基芴基中的一种。
其特征在于所述所述化合物的具体结构为：
Figure PCTCN2017102008-appb-000008
Figure PCTCN2017102008-appb-000009
Figure PCTCN2017102008-appb-000010
Figure PCTCN2017102008-appb-000011
Figure PCTCN2017102008-appb-000012
Figure PCTCN2017102008-appb-000013
Figure PCTCN2017102008-appb-000014
Figure PCTCN2017102008-appb-000015
Figure PCTCN2017102008-appb-000016
Figure PCTCN2017102008-appb-000017
中的任一种。
本申请人还提供了一种含有所述有机电致发光化合物的有机电致发光器件，所述化合物作为发光层掺杂材料应用于有机电致发光二极管。
所述有机电致发光化合物作为发光层掺杂材料时，所述有机电致发光器件具有下列通式(a)表示的化合物作为主体材料：
Figure PCTCN2017102008-appb-000018
通式(a)中，R1-R4、R7-R10分别独立的表示为氢原子、C1-C10的烷基或环烷基、取代或者未取代的芳香基、杂芳基；
其中n，m分别独立的选取0-3的整数，但不等同时为0；
R5、R6分别独立的表示取代或者未取代的芳香基或者杂芳基。
本发明有益的技术效果在于：
本发明所述化合物可应用于OLED发光器件制作，并且可以获得良好的器件表现，所述化合物作为OLED发光器件的独立的发光层材料、或者发光层掺杂材料使用时，器件的发光效率，功率效率和外量子效率均得到很大改善；器件色纯度得到明显改善，器件寿命得到提升。本发明所述化合物在OLED发光器件中具有良好的应用效果，具有良好的产业化前景。
本发明以二苯并庚烯结构为核心，并通过骨架核心进行修饰，该类结构的分子具有较强的空间立体作用，能够有效降低分子间的聚集效应，抑制材料的结晶程度，同时该类分子具有良好的热稳定性和较高的荧光量子效率。因此，该类材料运用于有机发光二极管中，可以有效提高器件效率和寿命。
附图说明
图1为本发明化合物制成的OLED器件的示意图。
图中：1、透明基板层，2、ITO阳极层，3、空穴注入层，4、空穴传输层，5、 发光层，6、电子传输层，7、电子注入层，8、阴极反射电极层。
具体实施方式
为了更加清楚的了解本发明的技术手段和实用目的，通过列举实施例和比较例，同时辅以图片加以说明。
实施例1(化合物04)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000019
250ml的四口瓶，氮气保护下，加入0.01mol中间体A，0.025mol二苯胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.3％，收率62.2％。
元素分析结构(分子式C53H38N2O2)：理论值C,86.62；H,5.21；N,3.81；O,4.35测试值：C,86.67；H,5.16；N,3.80；O,4.37
实施例2(化合物08)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000020
250ml的四口瓶，氮气保护下，加入0.01mol中间体A，0.011mol双(4-叔丁基苯基)胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.6％，收率54.1％。
元素分析结构(分子式C62H55NO)：理论值C,89.71；H,6.68；N,1.69；O,1.93测试值：C,89.68；H,6.71；N,1.71；O,1.92
实施例3(化合物14)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000021
250ml的四口瓶，氮气保护下，加入0.01mol中间体A，0.025mol双(3,4-二甲基苯基)胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2.5(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.3％，收率57.8％。
元素分析结构(分子式C71H56N2O2)：理论值C,87.98；H,5.82；N,2.89；O,3.30测试值：C,87.89；H,5.84；N,2.80；O,3.47
实施例4(化合物22)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000022
250ml的四口瓶，氮气保护下，加入0.01mol中间体D，0.025mol双(4-叔丁基苯基)胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.6％，收率51.4％。
元素分析结构(分子式C82H80N2O)：理论值C,88.77；H,7.27；N,2.52；O,1.44
测试值：C,88.72；H,7.30；N,2.55；O,1.43
实施例5(化合物38)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000023
250ml的四口瓶，氮气保护下，加入0.01mol中间体A，0.025mol(3-二苯氨基)咔唑，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.5％，收率54.8％。
元素分析结构(分子式C77H52N4O2)：理论值C,86.82；H,4.92；N,5.26；O,3.00；
测试值：C,86.87；H,4.95；N,5.28；O,2.90。
实施例6(化合物43)
Figure PCTCN2017102008-appb-000024
250ml的四口瓶，氮气保护下，加入0.01mol中间体E，0.011mol化合物a，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.6％，收率61.2％。
元素分析结构(分子式C79H55N3O2)：理论值C,87.99；H,5.14；N,3.90；O,2.97。
测试值：C,87.95；H,5.17；N,3.95；O,2.93。
实施例7(化合物51)
Figure PCTCN2017102008-appb-000025
250ml的四口瓶，氮气保护下，加入0.01mol中间体F，0.011mol 9,9-二甲基-N，N-二苯基-9,10-二氢吖啶-2-胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.6％，收率54.5％。
元素分析结构(分子式C66H46N2O2)：理论值C,88.17；H,5.16；N,3.12；O,3.56。
理论值C,88.20；H,5.14；N,3.15；O,3.51。
实施例8(化合物58)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000026
250ml的四口瓶，氮气保护下，加入0.01mol中间体G，0.025mol二苯胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.1％，收率59.5％。
元素分析结构(分子式C53H38N2O3)：理论值C,84.78；H,5.10；N,3.73；O,6.39理论值C,84.82；H,5.11；N,3.76；O,6.31
实施例9(化合物70)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000027
250ml的四口瓶，氮气保护下，加入0.01mol中间体H，0.025mol双(4-叔丁基苯基)胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC) 为98.2％，收率57.8％。
元素分析结构(分子式C53H38N2O3)：理论值C,86.67；H,4.62；N,3.21；O,5.50
理论值C,86.70；H,4.65；N,3.24；O,5.41
实施例10(化合物73)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000028
0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.9％，收率57.6％。
元素分析结构(分子式C83H60N2O5)：理论值C,85.54；H,5.19；N,2.40；O,6.86理论值C,85.44；H,5.21；N,2.44；O,6.91
实施例11(化合物109)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000029
250ml的四口瓶，氮气保护下，加入0.01mol中间体I，0.025mol二苯胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:2.5(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为97.2％，收率55.0％。
元素分析结构(分子式C53H38N2O4)：理论值C,83.01；H,4.99；N,3.65；O,8.35。
理论值C,83.06；H,5.03；N,3.68；O,8.23
实施例12(化合物118)
现提供该化合物的具体合成路线：
Figure PCTCN2017102008-appb-000030
250ml的四口瓶，氮气保护下，加入0.01mol中间体J，0.025mol二苯胺，0.03mol叔丁醇钠，1×10-4mol Pd2(dba)3，1×10-4mol三叔丁基膦，150ml甲苯，加热回流20小时，反应完全；自然冷却，过滤，滤液旋蒸，过硅胶柱，用甲苯:乙醇＝1:3(体积比)混合溶剂打浆，重结晶后白色固体，纯度(HPLC)为98.3％，收率57.4％。
元素分析结构(分子式C63H40N2O4)：理论值C,85.11；H,4.54；N,3.15；O,7.20
理论值C,85.14；H,4.50；N,3.20；O,7.16
发明化合物可以作为发光层掺杂材料使用。对本发明化合物14、化合物108、现有材料MQAB分别进行热稳定性、荧光量子效率、循环伏安稳定性的测定，检测结果如表1所示。
表1
化合物 Tg(℃) Td(℃) 荧光量子效率 循环伏安特性
化合物14 130 450 95％ 优
化合物108 122 435 90％ 优
MQAB 102 394 85％ 差
注：热失重温度Td是在氮气气氛中失重1％的温度，在日本岛津公司的TGA-50H热重分析仪上进行测定，氮气流量为20mL/min；Tg日本岛津公司的DSC-60热差扫描分析仪进行测定，氮气流量10mL/min。荧光量子效率采用日本HAMAMATSU公司的Quantaurus-QY(C13534-11)进行鉴定；循环伏安稳定性是通过循环伏安法观测材料的氧化还原特性来进行鉴定；测试条件：测试样品溶于体积比为2:1的二氯甲烷和乙腈混合溶剂，浓度1mg/mL，电解液是0.1M的四氟硼酸四丁基铵或六氟磷酸四丁基铵的有机溶液。参比电极是Ag/Ag+电极，对电极为钛板，工作电极为ITO电极，循环次数为20次。
由上表数据可知，本发明化合物具有较好的氧化还原稳定性，较高的热稳定性和荧光量子效率，可作为发光层掺杂材料使用，从而提升OLED器件效率和 寿命。
以下通过对比例1、2和实施例13～27详细说明本发明合成的材料在OLED器件上的应用效果。所述实施例13～24与对比例1、2相比，所述器件的制作工艺完全相同，并且所采用了相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是对器件中所使用的部分材料进行了一些调整，对比例1、2使用了本发明所述部分OLED材料。
对比例1
透明玻璃基板1采用透明材料。对ITO阳极层2(膜厚为150nm)进行洗涤，即依次进行碱洗涤、纯水洗涤、干燥后再进行紫外线-臭氧洗涤以清除透明ITO表面的有机残留物。
在进行了上述洗涤之后的ITO阳极层2上，利用真空蒸镀装置，蒸镀HAT-CN，其膜厚为10nm，这层有机材料作为空穴注入层3使用。紧接着蒸镀70nm厚度的TCTA(4,4',4″-三(咔唑-9-基)三苯胺)作为空穴传输层4。
上述空穴传输材料蒸镀结束后，制作OLED发光器件的发光层5，其结构包括OLED发光层5所使用材料mCP作为主体材料，MQAB作为掺杂材料，掺杂比例为4％重量比，发光层膜厚为25nm。
在上述发光层5之后，继续真空蒸镀电子传输层材料为TPBi。该材料的真空蒸镀膜厚为35nm，此层为电子传输层6。
在电子传输层6上，通过真空蒸镀装置，制作膜厚为1nm的氟化锂(LiF)层，此层为电子注入层7。
在电子注入层7上，通过真空蒸镀装置，制作膜厚为80nm的铝(Al)层，此层为阴极反射电极层8使用。各层材料结构如下所示：
Figure PCTCN2017102008-appb-000031
Figure PCTCN2017102008-appb-000032
所制作的OLED发光器件器件结构如表2所示，测试结果如表3所示。
如上所述地完成OLED发光器件后，用公知的驱动电路将阳极和阴极连接起来，测量器件的发光效率，发光颜色以及器件寿命(LT95：亮度衰减到初始亮度的95％)。
对比例2
TO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(NpPhAn和MQAB按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例13
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物04按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例14
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物08按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例15
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物14按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例16
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物22按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例17
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物38按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例18
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物43按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例19
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物51按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例20
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物58按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例21
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物70按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例22
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物73按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例23
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物109按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例24
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(mCP和化合物118按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例25
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(NpPhAn和化合物73按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例26
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(NpPhAn和化合物109按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
实施例27
ITO阳极层2/空穴注入层3(HAT-CN，厚度10nm)/空穴传输层4(TCTA，厚度70nm)/发光层5(NpPhAn和化合物118按照100:4的重量比混掺，厚度25nm)/电子传输层6(TPBi，厚度35nm)/电子注入层7(LiF，厚度1nm)/阴极反射电极层8(Al，厚度80nm)。
表2
Figure PCTCN2017102008-appb-000033
表3
器件代号 发光效(cd/A) 颜色 LT95寿命(H)
对比例1 3.0 蓝色 2.0
对比例2 3.6 蓝色 2.5
实施例13 3.8 蓝色 2.7
实施例14 4.0 蓝色 3.2
实施例15 4.1 蓝色 2.9
实施例16 3.9 蓝色 3.3
实施例17 4.3 蓝色 3.4
实施例18 4.5 蓝色 3.2
实施例19 4.6 蓝色 3.1
实施例20 4.2 蓝色 3.6
实施例21 4.8 蓝色 2.7
实施例22 5.0 蓝色 3.0
实施例23 4.5 蓝色 3.2
实施例24 3.5 蓝色 2.9
实施例25 5.3 蓝色 3.0
实施例26 5.1 蓝色 3.3
实施例27 5.4 蓝色 3.3
注：以上数据都是以对比例1作为标准器件，对比例1的电流效率为3.0cd/A(@10mA/cm2)；CIE色坐标为(0.15，0.15)；1000亮度下LT95寿命衰减为2Hr。寿命测试系统为本发明所有权人与上海大学共同研究的OLED器件寿命测试仪。
由表3的结果可以看出，本发明所述化合物可应用于OLED发光器件制作，并且可以获得良好的器件表现。器件的发光效率、外量子效率均得到很大改善；同时器件寿命提升非常明显。本发明所述化合物在OLED发光器件中具有良好的应用效果，并具有良好的产业化前景。
虽然已通过实施例和优选实施方式公开了本发明，但应理解，本发明不限于所公开的实施方式。相反，本领域技术人员应明白，其意在涵盖各种变型和类似的安排。因此，所附权利要求的范围应与最宽的解释相一致以涵盖所有这样的变型和类似的安排。

Claims (8)

  1. 一种有机电致发光化合物，其特征在于所述化合物的结构如通式(1)所示：
    Figure PCTCN2017102008-appb-100001
    通式(1)中，R1、R2分别独立的由通式(2)表示，R1、R2可以相同也可以不同；
    Figure PCTCN2017102008-appb-100002
    通式(2)中，a选自
    Figure PCTCN2017102008-appb-100003
    中的一种；
    X1、X2、X3分别独立的表示为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
    X4、X5分别独立的表示为碳原子数1-6的烷基、或苯基；或者X4、X5通过键结形成碳原子数为10-16的芳基环；
    R1中的a与C1-C2键、C2-C3键、或C3-C4连接成环；R2中的a与C5-C6键、C6-C7键、或C7-C8键连接成环；
    R3、R4分别独立的表示为碳原子数1-6的烷基、或苯基；或者R3、R4通过键结形成碳原子数为10-16的芳基环；
    R5独立地表示为取代或者未取代芳胺基、取代或者未取代的含氮杂芳基中的一种。
  2. 根据权利要求1所述的有机电致发光化合物，其特征在于所述化合物选 自通式通式(3)-(5)的任一种：
    Figure PCTCN2017102008-appb-100004
    其中R5、R6独立地表示为取代或未取代芳胺基、取代或未取代的含氮杂芳基。
  3. 根据权利要求1或2所述的有机电致发光化合物，其特征在于所述R5、R6分别独立的采用通式(6)或(7)表示：
    Figure PCTCN2017102008-appb-100005
    通式(6)、(7)中，X6为氧原子、硫原子、C1-10直链或支链烷基取代的亚烷基、芳基取代的亚烷基、烷基或芳基取代的叔胺基中的一种；
    R7、R8分别独立的表示为氢、碳原子数1-6的烷基、芳基、芳胺基；但至少有一个表示为芳胺基。
  4. 根据权利要求1或2所述的有机电致发光化合物，其特征在于所述R5、R6分别独立的采用通式(8)表示：
    Figure PCTCN2017102008-appb-100006
    Figure PCTCN2017102008-appb-100007
    其中，R9、R10分别独立的表示为芳基、或杂芳基。
  5. 根据权利要求3或4所述的有机电致发光化合物，其特征在于所述R7、R8、R9、R10分别独立的表示为取代或未取代的苯基、吡啶基、二联苯基、三联苯基、萘基、蒽基、菲基、三嗪基、嘧啶基、喹啉基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、或9,9-二苯基芴基中的一种。
  6. 根据权利要求1所述的有机电致发光化合物，其特征在于所述化合物的具体结构为：
    Figure PCTCN2017102008-appb-100008
    Figure PCTCN2017102008-appb-100009
    Figure PCTCN2017102008-appb-100010
    Figure PCTCN2017102008-appb-100011
    Figure PCTCN2017102008-appb-100012
    Figure PCTCN2017102008-appb-100013
    Figure PCTCN2017102008-appb-100014
    Figure PCTCN2017102008-appb-100015
    Figure PCTCN2017102008-appb-100016
    Figure PCTCN2017102008-appb-100017
    中的任一种。
  7. 一种含有所述有机电致发光化合物的有机电致发光器件，其特征在于所述化合物作为发光层掺杂材料应用于有机电致发光二极管。
  8. 根据权利要求书7所述有机电致发光器件，其特征在于所述有机电致发光化合物作为发光层掺杂材料时，所述有机电致发光器件具有下列通式(a)表示的化合物作为主体材料：
    Figure PCTCN2017102008-appb-100018
    通式(a)中，R1-R4、R7-R10分别独立的表示为氢原子、C1-C10的烷基或环烷基、取代或者未取代的芳香基、杂芳基；
    其中n，m分别独立的选取0-3的整数，但不等同时为0；
    R5、R6分别独立的表示取代或者未取代的芳香基或者杂芳基。
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