WO2020020178A1 - 一种有机电致发光材料及其应用 - Google Patents

一种有机电致发光材料及其应用 Download PDF

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WO2020020178A1
WO2020020178A1 PCT/CN2019/097340 CN2019097340W WO2020020178A1 WO 2020020178 A1 WO2020020178 A1 WO 2020020178A1 CN 2019097340 W CN2019097340 W CN 2019097340W WO 2020020178 A1 WO2020020178 A1 WO 2020020178A1
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organic compound
compound
organic
compound according
formula
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French (fr)
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高文正
魏金贝
邵爽
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北京鼎材科技有限公司
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    • C07D209/82—Carbazoles; Hydrogenated carbazoles
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Definitions

  • the invention relates to an organic compound, which can be used as a light-emitting material of an organic electroluminescent device; the invention also relates to the application of the compound in an organic electroluminescent device.
  • organic electroluminescent materials Under electro-excitation conditions, organic electroluminescent materials will produce 25% singlet states and 75% triplets.
  • Traditional fluorescent materials can only use singlet excitons due to spin inhibition.
  • triplet excitons researchers have proposed many methods, the most notable of which is the use of phosphorescent materials.
  • the phosphorescent material has a T1 life of more than 1 ⁇ s, which is much longer than the lifetime of the fluorescent material. It has a significant efficiency roll-off at high current density.
  • the use of rare heavy metals makes the material more expensive, which is not conducive to it. Reduced product costs.
  • Thermally activated delayed fluorescence (TADF) materials based on triplet-single-state transitions discovered by Professor Adachi of Kyushu University in Japan can use ambient heat to achieve reverse intersystem crossing of energy from triplet-excited to singlet-excited states without the need to use high Cost of rare metals can achieve high luminous efficiency.
  • TADF Thermally activated delayed fluorescence
  • TSF thermally activated sensitized delayed fluorescence
  • Patent Document 2 discloses an organic electroluminescence device including an anode, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode stacked on each other, and is characterized in that the triplet state and singlet state energy of the host material of the light emitting layer The level difference is less than 0.15eV, and the host material is doped with a fluorescent dye, and the singlet energy level of the fluorescent dye is lower than the singlet energy level of the host material, achieving high efficiency and low efficiency roll-off and more Good color purity.
  • the thermally activated delayed fluorescence process can be divided into several parts: the radiative and non-radiative transitions of the singlet exciton, the non-radiative transition of the T1 triplet exciton, the intersystem crossing (ISC) process of the exciton, and the reverse Intersystem Crossover (RISC) process.
  • the RISC process is the core of the entire TADF process.
  • the efficiency of the RISC process directly determines the utilization of T1.
  • designing and developing materials with high RISC rates has been the focus of research. At present, a variety of benzene cyanide materials have been reported.
  • Patent Document 1 CN102648268B;
  • Patent Document 2 CN102709485B
  • the sublimation temperature of the thermally activated delayed fluorescent material in the prior art is generally high, resulting in high energy consumption and reduced stability, which is not suitable for use in practical industries.
  • TADF materials are expected to make breakthroughs in blue light materials, but currently there is a problem of short life. Therefore, the existing TADF materials still have much room for improvement in terms of light emission performance.
  • the main object of the present invention is to provide a benzonitrile compound having thermally activated delayed fluorescence performance for an organic electroluminescence device, its application in the field of organic electroluminescence, and its use as a light-emitting layer material.
  • Electroluminescent device As described above, in order to obtain high luminous efficiency and good device stability in an organic electroluminescent device, it is necessary to develop a material having a high RISC rate and a low sublimation temperature.
  • the main object of the present invention is to provide a benzonitrile compound having thermally activated delayed fluorescence performance for an organic electroluminescence device, its application in the field of organic electroluminescence, and its use as a light-emitting layer material. Electroluminescent device.
  • the invention provides a compound of general formula, which has a structural formula represented by formula (1):
  • R 1 is selected from CN, CF 3 , and NO 2 ; m is an integer of 0 to 2, and n is an integer of 2 to (5-m);
  • Ar 1 is selected from hydrogen, halogen, C1 to C8 alkyl, C5 to C10 cycloalkyl, C1 to C8 alkoxy, substituted or unsubstituted C6 to C14 aryl, and substituted or unsubstituted C3 to A heteroaryl group of C12, a plurality of Ar 1 may be the same or different;
  • Ar 2 has a structural formula as shown in formula (2), and a plurality of Ar 2 may be the same or different;
  • X is selected from a single bond, O, S, NR 8 , CR 9 R 10 ; * represents the position where Ar 2 is connected to the benzene ring in formula (1);
  • R 2 to R 7 are each independently selected from hydrogen or an electron-donating substituent of C1 to C14, and at least one non-tertiary carbon branched alkyl group of C3 to C12; any adjacent two of R 2 to R 7 Can be looped
  • R 8 to R 10 are each independently selected from hydrogen, halogen, carbonyl, C1 to C8 alkyl, C5 to C10 cycloalkyl, C1 to C8 alkoxy, and substituted or unsubstituted C6 to C14 aryl , Substituted or unsubstituted C3-C12 heteroaryl, or a combination thereof.
  • the "electron substituent” and “functional group of the electron donor” in this specification refer to a group that increases the electron cloud density on the benzene ring after the group replaces hydrogen on the benzene ring.
  • the group include, but are not limited to: alkyl groups such as methyl and isopropyl; alkoxy groups such as methoxy; cycloalkyl groups such as cyclohexyl; substituted or unsubstituted aryl groups such as phenyl, anthracenyl, and phenanthrene Group; substituted or unsubstituted heteroaryl such as pyridyl and the like.
  • substituted or unsubstituted group described in this specification is substituted with one or more substituents selected from the group consisting of halogen, C1-C10 alkyl group, and C3-C10 cycloalkyl group when substituted. , C1-C10 alkoxy, C6-C14 aryl, and C3-C15 heteroaryl.
  • the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.
  • phenylcyano group refers to a group of groups represented by benzocyano groups and having a strong electron withdrawing ability (such as CN, CF 3 , NO 2 etc.) connected to a benzene ring group.
  • the inventors of the present application have further studied and found that the introduction of a non-tertiary carbon branched alkyl group into Ar 2 of the compound of the general formula of the present invention can improve the efficiency of an organic electroluminescent device using the compound, and it is even more surprising that The introduction of non-tertiary carbon branched alkyl groups can also significantly reduce the sublimation temperature of the resulting material. The reason is not clear. It is speculated that the introduction of branched alkyl groups with non-tertiary carbon can make the material maintain a large distance between molecules in the thin film state, avoiding the Dexter transfer of energy, thereby reducing energy quenching and improving efficiency. And lower the sublimation temperature.
  • R 3 and R 6 are a non-tertiary carbon branched alkyl group of C3 to C12, and it is more preferable that at least one of R 3 and R 6 is isopropyl group or sec-butyl group. Most preferably R 3 and R 6 are both isopropyl or sec-butyl.
  • R 3 and R 6 as the above-mentioned group, the efficiency of the organic electroluminescent device using the compound can be further improved, the sublimation temperature of the obtained material can be reduced, and at the same time, the device life can be improved.
  • R 2 to R 7 are preferably selected from the following groups:
  • Ar 1 is preferably selected from the following groups:
  • Ar 1 is more preferably selected from hydrogen, methyl, phenyl, and pyridyl.
  • Ar 1 As the above group, the stability of the compound can be improved, and the life of a device using the compound can be improved.
  • R 1 is preferably a cyano group.
  • the inventors of the present application have found that by limiting R 1 to a cyano group, the organic electroluminescent device using the compound has high efficiency and high stability. The reason is not clear. It is speculated that it may be because when R 1 is a cyano group, the organic compound of the present invention uses a phenylcyano group as the mother core, and introduces a functional group of an electron donor and a ⁇ -electron-deficient aromatic mother core skeleton.
  • the connection can form a material with intramolecular charge migration; in this compound, the highest occupied energy level and the lowest unoccupied energy level electron cloud are separated to form a thermally activated delayed fluorescent material, which can increase the RISC rate of the material and make the triplet state Energy levels are effectively used.
  • R 2 , R 4 , R 5 , and R 7 are hydrogen.
  • the present invention also provides an application of the compound as described above in an organic electroluminescent device.
  • the compound of the present invention is preferably used as a luminescent dye in an organic electroluminescent device.
  • the present invention also provides an organic electroluminescent device including a first electrode, a second electrode, and a plurality of organic layers interposed between the first electrode and the second electrode.
  • the organic layer It includes at least one light-emitting layer, and the organic layer contains a compound represented by the general formula (1), and the compound is preferably used as a luminescent dye or a sensitizer.
  • the compound of the general formula of the present invention which uses a benzocyano group as the mother core, and introduces a functional group of an electron donor, is connected to the ⁇ -electron-deficient aromatic mother core skeleton, and can form a material having intramolecular charge migration.
  • the highest occupied energy level of the compound is separated from the lowest unoccupied energy level of the electron cloud, forming a thermally activated delayed fluorescent material, increasing the RISC rate of the material, and effectively using the triplet energy level of the material. It can be used as a light-emitting material for an organic light-emitting layer.
  • Another important feature of the compounds of the general formula of the present invention is that the introduction of branched alkyl groups of non-tertiary carbon can keep the distance between the molecules in a thin film state, avoiding the Dexter transfer of energy, thereby reducing energy quenching. Improve the device efficiency; more importantly, experiments have found that the sublimation temperature of the material decreases significantly due to the introduction of branched alkyl groups of non-tertiary carbon. Since the current device preparation method is an evaporation process, a reduction in sublimation temperature will greatly reduce power consumption during use, and avoid material preparation under high temperature conditions, which will be beneficial to the commercial application of materials.
  • the compound of the present invention has a high triplet energy level, and can be used as a sensitizer material of an organic light-emitting layer to effectively transfer energy to the dye molecules to emit light, thereby achieving narrow-spectrum light emission.
  • the separation from radiation emission is beneficial to the reduction of the device's efficiency roll-off and the improvement of the device's life.
  • the compounds of the synthetic methods not mentioned in the present invention are all commercially available starting materials.
  • Various chemicals used in the examples such as petroleum ether, ethyl acetate, n-hexane, toluene, dichloromethane, potassium phosphate, sodium tert-butoxide, N-bromosuccinimide, methoxymethyl trimethyl Rhenium chloride, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, 1,3-bisdiphenylphosphinepropane nickel chloride, carbazole, 3,6-di-tert-butyl Basic chemical raw materials such as carbazole can be purchased in the domestic chemical product market.
  • reaction process is the same as that of compound M1, except that the raw material bis (4-isopropyl) aniline is replaced with bis (4-sec-butyl) aniline.
  • the other reaction conditions are unchanged, and compound M2 is obtained with a yield of 68%.
  • reaction process is the same as that of compound C1, except that 2,4-difluorobenzonitrile is replaced by 2,4,6-trifluorobenzonitrile, intermediate M1 is replaced by intermediate M2, and other reaction conditions are unchanged.
  • Compound C6 is obtained. Yield 82%.
  • reaction process is the same as that of compound C1, except that 2,4-difluorobenzonitrile is replaced by intermediate M3, and other reaction conditions are unchanged, and compound C15 is obtained with a yield of 72%.
  • the compound of this invention can be obtained by the said synthetic method, It is not limited to these methods. Those skilled in the art can also choose other methods, such as Stille coupling method, Grignard reagent method, Kumada-Tamao and other known methods. Any equivalent synthetic method can be used to achieve the purpose of preparing the target compound, which can be selected according to needs.
  • the obtained compounds are sublimated using the sublimation purification process before device preparation.
  • the purification equipment is the company's EMT-50-X purification equipment.
  • the specific operation process is as follows:
  • the sublimation temperature of the compound C7 in Example 1 was 310 degrees Celsius
  • the sublimation temperature of the compound CC-2 in Comparative Example 1 was 360 ° C. This may be due to the introduction of branched alkyl groups of non-tertiary carbon, which makes the compound loose in the state of vacuum sublimation, which makes it easy to sublime.
  • the device is prepared at a lower temperature in the device evaporation process, which is conducive to power consumption. Reduced, and the compound completes the evaporation process at a lower temperature, which can avoid material cracking caused by the high temperature state for a long time, which is beneficial to the stability of the device quality.
  • the organic light emitting diode includes a first electrode and a second electrode on the substrate, and an organic material located between the electrodes.
  • the first electrode and the second electrode include a hole transport layer, a light emitting layer, and an electron transport layer.
  • the substrate is a substrate used in an organic light emitting display, such as glass, polymer materials, and glass and polymer materials with TFT components.
  • the anode material can be transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO), or silver and its alloys, aluminum and its alloys.
  • the material may also be an organic conductive material such as PEDOT, and a multilayer structure of the above materials.
  • the device may further include a hole injection layer located between the hole transport layer and the anode, including but not limited to one or more combinations of HI-1 to HI-3 listed below.
  • the hole transport layer may include, but is not limited to, a combination of one or more of HT-1 to HT-31 listed below.
  • the light-emitting layer host material may include, but is not limited to, one or more combinations of TDH1-TDH24 listed below.
  • the phosphorescent dye may include, but is not limited to, a combination of one or more of PD-1 to PD-17 listed below.
  • the fluorescent dye may include, but is not limited to, a combination of one or more of FD1-FD18 listed below.
  • the electron transport layer may include, but is not limited to, a combination of one or more of ET-1 to ET-57 listed below.
  • the device may further include an electron injection layer between the electron transport layer and the cathode, and the material of the electron injection layer includes but is not limited to one or more combinations listed below.
  • the cathode is a magnesium-silver mixture, LiF / Al, ITO and other metals, metal mixtures, and oxides.
  • Examples 1-8 and Comparative Examples 1-2 The effects of the compounds synthesized by the present invention in the light-emitting layer dyes are described in detail in Examples 1-8 and Comparative Examples 1-2.
  • Examples 9-10 and Comparative Examples 3-4 illustrate the effects of the compounds synthesized in the present invention on devices. Effect of the sensitizer applied to the light-emitting layer; the manufacturing process of the device is the same, and the same substrate material and electrode material are used, and the film thickness of the electrode material remains the same, except that the light-emitting layer material of the device has occurred Variety.
  • the molecular formula of the comparative compound used is as follows:
  • the organic electroluminescent device is prepared as follows:
  • the glass plate coated with the transparent conductive layer of ITO was sonicated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone: ethanol, and baked in a clean environment to completely remove water. Light and ozone cleaning and bombarding the surface with a low-energy cation beam;
  • the above glass substrate with anode was placed in a vacuum chamber, and evacuated to 1 ⁇ 10 -5 to 9 ⁇ 10 -3 Pa, and HI-2 was vacuum-evaporated on the anode layer film as a hole injection layer.
  • the plating rate is 0.1nm / s, and the thickness of the deposited film is 10nm;
  • HT-2 was vacuum-deposited on the hole injection layer as a hole transport layer of the device, and the deposition rate was 0.1 nm / s, and the total film thickness was 40 nm;
  • HT-28 was vacuum deposited on the hole transport layer as the second hole transport layer of the device, the deposition rate was 0.1 nm / s, and the total film thickness was 20 nm;
  • the light-emitting layer of the device is vacuum-evaporated on the hole-transport layer.
  • the light-emitting layer includes a host material and a dye material.
  • the host material TDH14 evaporation rate is adjusted to 0.1 nm / s, and the dye C2 evaporation rate is adjusted. 20% ratio setting, the total film thickness of evaporation is 30nm;
  • the electron transport layer material ET-34 of the device was vacuum-evaporated on the light-emitting layer, and the evaporation rate was 0.1 nm / s, and the total film thickness was 30 nm;
  • LiF with a thickness of 0.5 nm was vacuum-deposited on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm was used as a cathode of the device.
  • ETL electron transport layer
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C3 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C6 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C7 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C11 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C15 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C17 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% C36 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al ( 150nm)
  • the device is prepared according to the method described above, except that the light-emitting layer includes a host material, a sensitizer material, and a dye material.
  • the TDH-14 evaporation rate of the host material is adjusted to 0.1 nm / s by using a multi-source co-evaporation method.
  • the evaporation rate of the sensitizer body C7 is 20% of the evaporation rate of the host material, and the evaporation rate of the dye FD-14 is set to 3% of the evaporation rate of the host material.
  • the total evaporation thickness is 30nm; It has the following structure:
  • the device is prepared according to the method described above.
  • the light-emitting layer includes a host material, a sensitizer material, and a dye material.
  • the host material TDH14 evaporation rate is adjusted to 0.1 nm / s.
  • the evaporation rate of the chemical agent body C7 is 20% of the evaporation rate of the host material, and the evaporation rate of the dye PD-1 is set to 3% of the evaporation rate of the host material.
  • the total evaporation thickness is 30nm;
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH-14 20%
  • C7 3%
  • PD-1 30nm
  • ET-34 20nm
  • LiF 0.5nm
  • Al 150nm
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% CC-1 (30nm)
  • ET-34 20nm
  • LiF 0.5nm
  • Al 150nm
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH14 20% CC-2 (30nm) / ET-34 (20nm) / LiF (0.5nm) / Al (150nm)
  • ITO 150nm
  • HI-2 10nm
  • HT-2 40nm
  • HT-28 20nm
  • TDH-14 20%
  • CC-2 3%
  • PD-1 30nm
  • ET-34 20nm
  • LiF 0.5nm
  • Al 150nm
  • the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1 to 10 and Comparative Examples 1 to 4 and the lifetime of the devices were measured using a digital source meter and a luminance meter. Specifically, the voltage is increased at a rate of 0.1V per second, and the driving voltage is measured when the brightness of the organic electroluminescent device reaches the required brightness, and the current density at this time is measured; the ratio of the brightness to the current density is Current efficiency; LT80's life test is as follows: Use a luminance meter to maintain a constant current at the required brightness, and measure the time for the brightness of the organic electroluminescent device to fall to 80% of the initial brightness, in hours. The results are shown in Table 1.
  • Example 1-8 Comparative Example 1-2
  • the compound synthesized by the present invention has a greater improvement in efficiency and lifetime than the known OLED materials when applied to the light-emitting layer dye in the device, especially the lifetime is significantly improved.
  • the reason is not clear, it is presumed as follows: In Comparative Examples 1 and 2, the above CC-1 and CC-2 were used as the light-emitting layer dyes, respectively, but CC-1 and CC-2 did not introduce the present compound into Ar 2 of the general compound.
  • Examples 9-10 and Comparative Examples 3-4 show that when the compound synthesized by the present invention is applied to a light-emitting layer sensitizer in a device, it can effectively sensitize the dye and achieve effective energy transfer, thereby obtaining excellent device performance. .

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Abstract

一种式（1）所示的有机化合物，其中Ar 2具有如式（2）所示的结构式，多个Ar 2可以相同或不同。式（1）所示的化合物可以用作有机电致发光器件的发光层材料，其具备热活化延迟荧光性能。

Description

一种有机电致发光材料及其应用 技术领域
本发明涉及一种有机化合物，其可以用作有机电致发光器件发光材料；本发明还涉及该化合物在有机电致发光器件中的应用。
背景技术
在电致激发的条件下，有机电致发光材料会产生25％的单线态和75％的三线态，传统的荧光材料由于自旋禁阻的原因只能利用单线态激子。为了利用三线态激子，研究者提出了许多方法，其中最为显著的是磷光材料的利用。然而磷光材料由于T1寿命一般在1μs以上，远远高于荧光材料几十纳秒的寿命，因此在高电流密度下效率滚降严重，而且由于使用了稀有的重金属，材料较为昂贵，因此不利于产品成本的降低。
日本九州大学的Adachi教授发现的基于三线态-单线态跃迁的热激活延迟荧光(TADF)材料利用环境热量可实现能量从三线态激发态向单线态激发态的逆向系间窜越，无需使用高成本的稀有金属即可实现高发光效率。在专利文献1中，新日铁住金化学株式会社和九州大学揭示了一种基于吲哚并咔唑的材料(参见下图)，并揭示了一种荧光及延迟荧光型的有机发光元件，其特征在于，在基板上具有至少一个发光层含有发射荧光及延迟荧光的有机发光材料，所述发光材料的激发单重态能量和激发三重态能量的差为0～0.2eV，表示化合物展示了较高的效率性能。
Figure PCTCN2019097340-appb-000001
清华大学段炼教授提出的热活化敏化延迟荧光(TASF)的发光机理的重点是将激发态三线态能量通过上转换至激发态单重态能量，然后通过Foxter能量转移至染料激发态单重态，再实现发光，从而实现了能量采集和发光过程的分离。在专利文献2揭示了一种有机电致发光器件，包括彼此层叠的阳极、空穴传输层、发光层、电子传输层及阴极，其特征在于，发光层的主体材料的三线态与单线态能级差小于0.15eV，且 在所述主体材料中掺杂荧光染料，并且所述荧光染料的单线态能级低于主体材料的单线态能级，实现了高的效率和低的效率滚降以及更好的色纯度。
热活化延迟荧光过程主要可以分为几个部分：单线态激子的辐射跃迁以及非辐射跃迁，T1三线态激子的非辐射跃迁过程，激子的系间窜越(ISC)过程以及反向系间窜越(RISC)过程。在这些过程中，RISC过程是整个TADF过程的核心。RISC过程的效率直接决定了T1的利用率。在有机电致发光材料的研究过程中，设计开发具有高RISC速率的材料一直是研究重点。目前，已有多种苯氰类材料见诸报道。
现有技术文献：
专利文献1：CN102648268B；
专利文献2：CN102709485B；
发明内容
发明要解决的问题
然而，现有技术中的热活化延迟荧光材料的升华温度普遍较高，导致高的能耗和稳定性降低，并不适合在实际工业中使用。此外，TADF材料有望在蓝光材料取得突破，但目前存在寿命过短的问题。因此，现有的TADF材料在发光性能方面还有很大改进余地。
解决问题的方案
如上所述，为了在有机电致发光器件中得到高的发光效率和好的器件稳定性，需开发具有高RISC速率和低升华温度的材料。有鉴于此，本发明的主要目的在于提供一种有机电致发光器件用的具有热活化延迟荧光性能的苯腈类化合物、其在有机电致发光领域的应用及采用其作为发光层材料的有机电致发光器件。
本发明提供了一种通式化合物，具有如式(1)所示的结构式：
Figure PCTCN2019097340-appb-000002
式(1)中，R 1选自CN、CF 3、NO 2；m为0～2的整数，n为2～(5-m)的整数；
Ar 1选自氢、卤素、C1～C8的烷基、C5～C10的环烷基、C1～C8的烷氧基、取代或未取代的C6～C14的芳基、取代或未取代的C3～C12的杂芳基，多个Ar 1可以相同或不同；Ar 2具有如式(2)所示的结构式，多个Ar 2可以相同或不同；
Figure PCTCN2019097340-appb-000003
式(2)中，X选自单键、O、S、NR 8、CR 9R 10；*表示Ar 2与式(1)中苯环连接的位置；
R 2-R 7各自独立地选自氢或C1～C14的供电子取代基，且至少有一个为C3～C12的非叔碳的支链烷基；R 2-R 7中任意相邻的二者可以成环；
R 8-R 10各自独立地选自氢、卤素、羰基、C1～C8的烷基、C5～C10的环烷基、C1～C8的烷氧基、取代或未取代的C6～C14的芳基、取代或未取代的C3～C12的杂芳基，或其组合。
在本说明书中，除非另有说明，否则下述术语具有如下含义：
本说明书中的“供电子取代基”、“供电子的功能基团”是指该基团取代苯环上的氢后，使苯环上的电子云密度升高的基团。所述基团可以列举但不限于：烷基如甲基、异丙基；烷氧基如甲氧基；环烷基如环己基；取代或未取代的芳基如苯基、蒽基、菲基；取代或未取代的杂芳基如吡啶基等。
本说明书中所述的“取代或未取代的”基团在被取代时被一个或多个选自以下基团的取代基取代：卤素、C1～C10的烷基、C3～C10的环烷基、C1～C10的烷氧基、C6～C14的芳基和C3～C15的杂芳基。
需要说明的是，本发明中，Ca～Cb的表达方式代表该基团具有的碳原子数为a～b，除非特殊说明，一般而言该碳原子数不包括取代基的碳原子数。
本申请发明人研究发现，以苯氰类基团作为母核，并引入供电子的功能基团，可以形成具有良好的延迟荧光性能的热活化延迟荧光材料，其具体结构如上所述。这里 所说的“苯氰类基团”是指以苯氰基团为代表的，具有强吸电子能力的基团(例如CN、CF 3、NO 2等)连接在苯环上的一类基团。本申请发明人进一步研究发现，向本发明通式化合物的Ar 2中引入非叔碳的支链烷基，能够提升使用了该化合物的有机电致发光器件的效率，更令人意外的是，非叔碳的支链烷基的引入还能使所得材料的升华温度明显降低。其原因尚不明确，据推测可能是由于非叔碳的支链烷基的引入能使材料在薄膜状态下分子间保持较大距离，避免能量的Dexter传递，从而减少能量淬灭，提升效率，并且降低了升华温度。
上述通式(1)中，优选R 3和R 6至少有一个为C3～C12的非叔碳的支链烷基，更优选R 3和R 6至少有一个为异丙基或仲丁基，最优选R 3和R 6均为异丙基或仲丁基。
通过将R 3和R 6设为如上基团，可以进一步提高使用了该化合物的有机电致发光器件的效率，降低所得材料的升华温度，同时还能提高器件寿命。
上述通式(1)中，R 2-R 7均优选选自以下基团：
Figure PCTCN2019097340-appb-000004
Ar 1优选选自以下基团：
Figure PCTCN2019097340-appb-000005
Ar 1更优选选自氢、甲基、苯基、吡啶基。
通过将Ar 1设为如上基团，可以提高化合物的稳定性，进而提高使用了该化合物的器件的寿命。
上述通式(1)中，R 1优选为氰基。
本申请发明人发现，通过将R 1限定为氰基，使用了该化合物的有机电致发光器件具有高效率和高稳定性。其原因尚不明确，据推测可能是由于R 1为氰基时，本发明的有机化合物以苯氰基团作为母核，通过引入供电子的功能基团与缺π电子型芳香性母核骨架连接，可以形成具有分子内电荷迁移的材料；在该化合物中，最高占有能级和最低未占有能级电子云分离，形成热活化延迟荧光材料，可以提高材料的RISC速率，使得材料的三线态能级得到有效利用。
上述通式(1)中，优选R 2、R 4、R 5、R 7均为氢。
作为本发明的新型通式化合物的优选例子，可举出选用下述代表性化合物C1～C39：
Figure PCTCN2019097340-appb-000006
Figure PCTCN2019097340-appb-000007
Figure PCTCN2019097340-appb-000008
Figure PCTCN2019097340-appb-000009
作为本发明的另一个方面，本发明还提供了一种如上所述的化合物在有机电致发光器件中的应用。本发明的化合物优选用于有机电致发光器件中的发光染料。
作为本发明的又一个方面，本发明还提供了一种有机电致发光器件，包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层，有机层中包括至少一层发光层，所述有机层中含有如通式(1)表示的化合物，优选上述化合物用作发光染料或敏化剂。
发明效果
本发明的新型通式化合物的优点在于：
(1)本发明的通式化合物，以苯氰基团作为母核，通过引入供电子的功能基团，与缺π电子型芳香性母核骨架连接，可以形成具有分子内电荷迁移的材料，化合物的最高占有能级和最低未占有能级电子云分离，形成热活化延迟荧光材料，提高材料的RISC速率，使得材料的三线态能级得到有效利用，用作有机发光层的发光材料，可提供具有高效率和高稳定性的有机电致发光器件；
(2)本发明的通式化合物的另一个重要特征是，非叔碳的支链烷基的引入能保持材料在薄膜状态下分子间距离较大，避免能量的Dexter传递，从而减少能量淬灭，提升器件效率；更重要的是，实验发现由于非叔碳的支链烷基的引入，材料的升华温度降低明显。由于目前器件制备方式为蒸镀工艺，升华温度的降低将使得在使用过程中极大减少功耗，和避免材料在高温条件下制备，这将有利于材料的商业化应用。
(3)本发明化合物具有较高的三线态能级，可用作有机发光层的敏化剂材料将能量有效的传递给染料分子进行发光，从而实现窄光谱发光，在此过程中由于能量采集和辐射发光实现分离，有利于器件的效率滚降的减小和器件寿命的提升。
具体实施方式
为了使本领域技术人员更好地理解本发明，下面结合具体实施方式对本发明作进一步详细说明。
本发明中未提到的合成方法的化合物的都是通过商业途径获得的原料产品。实施例中所用的各种化学药品如石油醚、乙酸乙酯、正己烷、甲苯、二氯甲烷、磷酸钾、叔丁醇钠、N-溴代丁二酰亚胺、甲氧甲基三甲基氯化鏻、三(二亚苄基丙酮)二钯、四(三苯基膦)钯、1,3-双二苯基膦丙烷氯化镍、咔唑、3,6-二叔丁基咔唑等基础化工原料均可在国内化工产品市场买到。
下面对本发明化合物的合成方法进行简要的说明。
合成实施例1
化合物C1的合成:
Figure PCTCN2019097340-appb-000010
中间体M1的制备：
氮气保护下，1000ml单口瓶中加入400ml新戊酸加热到50℃，在50℃下加入二(4-异丙基)苯胺(40g,0.158mol),醋酸钯(35.6g,0.158mol)，碳酸钾(21.8g,0.158mol)，升温至100摄氏度反应过夜，反应完毕，用二氯甲烷萃,二氯甲烷中加入饱和碳酸钾1000ml充分搅拌3小时，分液后，抽滤，有机相再用饱和食盐水2000ml洗一次，旋干，硅胶过柱，旋干洗脱液，用少量石油醚煮洗得16g,产品，收率40％，纯度99.9％，类白色固体。
化合物C1的制备：
氮气保护下，1000ml三口瓶中加入3.1g氢化钠，溶解在50mlDMF中，室温滴加3,6-二叔丁基咔唑的DMF溶液240ml，滴毕反应一小时再滴加2,4-二氟苯腈的DMF溶液120ml，升温至80℃反应过夜，降温后搅拌下倒入2000ml水中，析出大量黄绿色固体，用2000ml二氯甲烷溶解，分液，有机相水洗，干燥过硅胶柱，得19g白色固体，纯度99.61％，收率86％。
产物MS(m/e)：601.3， 1H NMR(500MHz,CDCl 3)δ8.96(s,2H),8.44(s,1H),8.19(s,2H),7.90(d,J＝30.0Hz,2H),7.46(d,J＝60.0Hz,4H),7.33(d,J＝0.8Hz,2H),7.15(s,2H),2.87(s,1H),1.20(s,26H).
化合物C3的合成:
Figure PCTCN2019097340-appb-000011
化合物C3的合成:
反应过程同化合物C1，只是将原料2,4-二氟苯腈换为2,3,5,6-四氟苯腈，其他反应条件不变，得化合物C3，收率为89％。
产物MS(m/e)：1099.6， 1H NMR(500MHz,CDCl 3)δ8.96(s,4H),8.91(s,1H),8.19(s,4H),7.46(d,J＝60.0Hz,9H),7.27(d,J＝8.9Hz,4H),7.15(s,4H),2.87(s,3H),1.20(s,51H).
化合物C6的合成:
Figure PCTCN2019097340-appb-000012
中间体M2的合成:
反应过程同化合物M1，只是将原料二(4-异丙基)苯胺换为二(4-仲丁基)苯胺，其他反应条件不变，得化合物M2，收率为68％。
化合物C6的合成:
反应过程同化合物C1，只是将2,4-二氟苯腈换为2,4,6-三氟苯腈，中间体M1换为中间体M2,其他反应条件不变，得化合物C6，收率为82％。
产物MS(m/e)：935.3， 1H NMR(500MHz,CDCl 3)δ8.96(s,4H),8.52(s,2H),8.19(s,4H),7.40(dd,J＝59.2,31.5Hz,11H),7.34(d,J＝3.0Hz,4H),7.34(d,J＝3.0Hz,4H),7.15(s,4H),2.55(s,4H),1.52(s,6H),1.16(s,22H),0.76(s,11H).
化合物C15的合成:
Figure PCTCN2019097340-appb-000013
中间体M3的合成：
室温下在一个装有磁力搅拌的1000mL三口烧瓶中加入4-溴-2,3,5,6-四氟苯氰10g(39.5mmol，1eq)；4-吡啶硼酸10.6g(86.9mmol，2.2eq)、四三苯基磷钯0.814g(0.79mmol，2％eq)、碳酸钾27g(237mmol，6eq)、1,4-二氧六环/水(400mL/100mL)，加毕，置换氮气3次，开启搅拌，油浴加热升温至回流(油浴温度120℃)反应6小时。TLC跟踪反应显示4-溴-2,3,5,6-四氟苯氰反应完全，停止反应。将反应液降至室温，分液，水相用EtOAc(100mL)萃取，合并有机相，饱和食盐水洗涤，无水硫酸钠干燥，过滤，减压旋干得灰色固体。用DCM溶解后上硅胶柱抽滤。减压旋干得类白色固体，用甲苯重结晶得到10.2g白色固体。HPLC99.56％，收率为88％。
化合物C15的合成：
反应过程同化合物C1，只是将2,4-二氟苯腈换为中间体M3，其他反应条件不变，得化合物C15，收率为72％。
产物MS(m/e)：1176.7， 1H NMR(500MHz,CDCl 3)δ8.96(s,4H),8.96(s,4H),8.71(s,2H),8.19(s,4H),7.90(s,2H),7.46(d,J＝60.0Hz,8H),7.30(d,J＝10.8Hz,4H),7.15(s,4H),2.87(s,3H),1.20(s,49H).
需要说明的是，本发明化合物可以由上述合成方法得到，但不限定于这些方法。 本领域技术人员也可以选取其他方法，例如Stille偶联法、格氏试剂法、Kumada-Tamao等已知的方法,任何等同的合成方法使用能实现目标化合物制备的目的，都可以根据需要选择。
升华提纯实施例
升华实施例1
所得化合物在器件制备前均采用升华提纯工艺制备升华品，提纯设备为本公司EMT-50-X级提纯设备。具体操作流程如下：
取1g化合物C7放置石英舟中，将石英舟放置入提纯设备，对设备抽真空，当真空度稳定在10 -2～10 -3Pa之间时，设置三个温区为100℃打开加热；
逐步提高温度控制，高温区、中温区和低温区保持适当温差，观察升华现象，待有少量薄膜产生时停止加热，保温至材料升华完毕；
打开炉盖待温度降至室温后，关闭泵，打开氮气，平衡大气压，取下氮气挡板，取出石英舟收料。
升华比较例1
采用与化合物C7的相同方法，将化合物C7替换为化合物CC-2。
Figure PCTCN2019097340-appb-000014
结果发现，实施例1中化合物C7的升华温度为310摄氏度，而比较例1中化合物CC-2的升华温度为360℃。这可能是由于非叔碳的支链烷基的引入使得化合物在真空升华状态下保持分子疏松，从而易于升华，在器件蒸镀工艺中采用较低的温度完成器件制备，从而有利于功耗的降低，且化合物在较低温度下完成蒸镀工艺，能避免材料由于长时间高温状态下导致的材料裂解，有利于器件品质的稳定。
器件实施例
有机发光二极管包括位于基板上的第一电极和第二电极，以及位于电极之间的有 机材料，第一电极和第二电极之间包括空穴传输层、发光层、电子传输层。
基板使用有机发光显示器所用的基板，例如：玻璃、聚合物材料以及带有TFT元器件的玻璃和聚合物材料等。
阳极材料可以采用铟锡氧(ITO)、铟锌氧(IZO)、二氧化锡(SnO 2)、氧化锌(ZnO)等透明导电材料，也可以是银及其合金、铝及其合金等金属材料，也可以是PEDOT等有机导电材料，及上述材料的多层结构。
器件中还可以包括位于空穴传输层与阳极之间的空穴注入层,包括但不限于以下所罗列的HI-1至HI-3的一种或多种的组合。
Figure PCTCN2019097340-appb-000015
空穴传输层可以包括但不限于以下所罗列的HT-1至HT-31的一种或多种的组合。
Figure PCTCN2019097340-appb-000016
Figure PCTCN2019097340-appb-000017
Figure PCTCN2019097340-appb-000018
发光层主体材料可以包括但不限于以下所罗列的TDH1-TDH24的一种或多种的组合。
Figure PCTCN2019097340-appb-000019
Figure PCTCN2019097340-appb-000020
磷光染料可以包括但不限于以下所罗列的PD-1至PD-17的一种或多种的组合。
Figure PCTCN2019097340-appb-000021
荧光染料可以包括但不限于以下所罗列的FD1-FD18的一种或多种的组合。
Figure PCTCN2019097340-appb-000022
电子传输层可以包括但不限于以下所罗列的ET-1至ET-57的一种或多种的组合。
Figure PCTCN2019097340-appb-000023
Figure PCTCN2019097340-appb-000024
Figure PCTCN2019097340-appb-000025
器件中还可以包括位于电子传输层与阴极之间的电子注入层，电子注入层材料包括但不限于以下罗列的一种或多种的组合。
LiQ,LiF,NaCl,CsF,Li2O,Cs 2CO 3,BaO,Na,Li,Ca。
阴极为镁银混合物、LiF/Al、ITO等金属、金属混合物、氧化物。
以下通过实施例1-8和比较例1-2详细说明本发明合成的化合物在器件中应用于发光层染料的效果；实施例9-10和比较例3-4说明本发明合成的化合物在器件中应用于发光层敏化剂主体的效果；所述器件的制作工艺相同，并且采用相同的基板材料和电极材料，电极材料的膜厚也保持一致，所不同的是器件的发光层材料发生了变化。所用到比较例化合物分子式如下：
Figure PCTCN2019097340-appb-000026
实施例1
有机电致发光器件制备过程如下：
将涂布了ITO透明导电层的玻璃板在商用清洗剂中超声处理，在去离子水中冲洗，在丙酮：乙醇混合溶剂中超声除油，在洁净环境下烘烤至完全除去水份，用紫外光和臭氧清洗，并用低能阳离子束轰击表面；
把上述带有阳极的玻璃基片置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述阳极层膜上真空蒸镀HI-2作为空穴注入层，蒸镀速率为0.1nm/s，蒸镀膜厚为10nm；
在空穴注入层之上真空蒸镀HT-2作为器件的空穴传输层，蒸镀速率为0.1nm/s，蒸镀总膜厚为40nm；
在空穴传输层之上真空蒸镀HT-28作为器件的第二空穴传输层，蒸镀速率为0.1nm/s，蒸镀总膜厚为20nm；
在空穴传输层之上真空蒸镀器件的发光层，发光层包括主体材料和染料材料，利用多源共蒸的方法，调节主体材料TDH14蒸镀速率为0.1nm/s，染料C2蒸镀速率20％比例设定，蒸镀总膜厚为30nm；
在发光层之上真空蒸镀器件的电子传输层材料ET-34，其蒸镀速率为0.1nm/s，蒸镀总膜厚为30nm；
在电子传输层(ETL)上真空蒸镀厚度为0.5nm的LiF作为电子注入层，厚度为150nm的Al层作为器件的阴极。
按照上文所述的方法制备以下各器件，使其具有以下结构：
实施例2：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C3(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
其中20％表示C3相对于TDH14的重量比为20％，以下实施例也按此方式表达。
实施例3：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C6(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例4：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C7(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例5：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C11(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例6：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C15(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例7：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C17(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例8：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％C36(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例9：
按照上文所述的方法制备器件，不同之处在于发光层包括主体材料、敏化剂材料和染料材料，利用多源共蒸的方法，调节主体材料TDH-14蒸镀速率为0.1nm/s，敏化剂主体C7的蒸镀速率为主体材料蒸镀速率的20％，染料FD-14的蒸镀速率为主体材料蒸镀速率的3％比例设定，蒸镀总膜厚为30nm；使其具有以下结构：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH-14:20％C7:3％FD-14(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
实施例10：
按照上文所述的方法制备器件，不同之处在于发光层包括主体材料、敏化剂材料和染料材料，利用多源共蒸的方法，调节主体材料TDH14蒸镀速率为0.1nm/s，敏化剂主体C7的蒸镀速率为主体材料蒸镀速率的20％，染料PD-1的蒸镀速率为主体材料蒸镀速率的3％比例设定，蒸镀总膜厚为30nm；使其具有以下结构：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH-14:20％C7:3％PD-1(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
比较例1：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％CC-1(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
比较例2：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH14:20％CC-2(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
比较例3：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH-14:20％CC-2:3％FD-14(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
比较例4：
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/HT-28(20nm)/TDH-14:20％CC-2:3％PD-1(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)
对由上述过程制备的有机电致发光器件进行如下性能测定：
在同样亮度下，使用数字源表及亮度计测定实施例1～10以及比较例1～4中制备得到的有机电致发光器件的驱动电压和电流效率以及器件的寿命。具体而言，以每秒0.1V的速率提升电压，测定当有机电致发光器件的亮度达到要求亮度时的电压即驱动电压，同时测出此时的电流密度；亮度与电流密度的比值即为电流效率；LT80的寿命测试如下：使用亮度计在要求亮度下，保持恒定的电流，测量有机电致发光器件的亮度降为80％初始亮度的时间，单位为小时。结果见表1。
表1有机电致发光器件性能
Figure PCTCN2019097340-appb-000027
通过实施例1-8和比较例1-2对比可见，本发明合成的化合物在器件中应用于发光层染料时无论是效率还是寿命都比已知OLED材料获得较大改观，特别是寿命提升明显。其原因尚不明确，据推测如下：比较例1和2中分别采用上述CC-1和CC-2作为发光层染料，而CC-1和CC-2没有向通式化合物的Ar 2中引入本发明所限定的非叔碳的支链烷基，因此相应的有机电致发光器件的效率较低；此外，由于实施例1-8使用的化合物中的Ar 1、R 3和R 6均为本发明中上述的优选基团，因此所得化合物的稳定性提高，所得器件寿命进一步增长。
实施例9-10和比较例3-4的对比说明本发明合成的化合物在器件中应用于发光层敏化剂时，可以有效敏化染料，能实现有效的能量传递，从而获得优异的器件性能。
以上结果表明，本发明的新型有机材料用于有机电致发光器件，可以有效提高器 件电流效率，且具有良好的稳定性能，提升器件寿命，是性能良好的有机电致发光材料。
尽管结合实施例对本发明进行了说明，但本发明并不局限于上述实施例，应当理解，在本发明构思的引导下，本领域技术人员可进行各种修改和改进，所附权利要求概括了本发明的范围。

Claims (10)

  1. 一种有机化合物，具有如式(1)所示的结构式：
    Figure PCTCN2019097340-appb-100001
    式(1)中，R 1选自CN、CF 3、NO 2；m为0～2的整数，n为2～(5-m)的整数；
    Ar 1选自氢、卤素、C1～C8的烷基、C3～C8的环烷基、C1～C8的烷氧基、取代或未取代的C6～C14的芳基、取代或未取代的C3～C12的杂芳基，多个Ar 1可以相同或不同；Ar 2具有如式(2)所示的结构式，多个Ar 2可以相同或不同；
    Figure PCTCN2019097340-appb-100002
    式(2)中，X选自单键、O、S、NR 8、CR 9R 10；*表示Ar 2与式(1)中苯环连接的位置；
    R 2-R 7各自独立地选自氢或C1～C14的供电子取代基，且至少有一个为C3～C12的非叔碳的支链烷基；R 2-R 7中任意相邻的二者可以成环；
    R 8-R 10各自独立地选自氢、卤素、羰基、C1～C8的烷基、C5～C10的环烷基、C1～C8的烷氧基、取代或未取代的C6～C14的芳基、取代或未取代的C3～C12的杂芳基，或其组合。
  2. 根据权利要求1所述的有机化合物，其中，R 3和R 6至少有一个为C3～C12的非叔碳的支链烷基。
  3. 根据权利要求2所述的有机化合物，其中，R 3和R 6至少有一个为异丙基或仲丁基。
  4. 根据权利要求3所述的有机化合物，其中，R 3和R 6均为异丙基或仲丁基。
  5. 根据权利要求1所述的有机化合物，其中，R 2-R 7选自以下基团：
    Figure PCTCN2019097340-appb-100003
  6. 根据权利要求1所述的有机化合物，其中，Ar 1选自以下基团：
    Figure PCTCN2019097340-appb-100004
    优选选自氢、甲基、苯基、吡啶基。
  7. 根据权利要求1所述的有机化合物，其中，R 1为氰基。
  8. 根据权利要求1或2所述的有机化合物，其为以下化合物C1～C39中的一种：
    Figure PCTCN2019097340-appb-100005
    Figure PCTCN2019097340-appb-100006
    Figure PCTCN2019097340-appb-100007
    Figure PCTCN2019097340-appb-100008
  9. 权利要求1～8中任一项所述的有机化合物在有机电致发光器件中的应用。
  10. 一种有机电致发光器件，包括第一电极、第二电极和插入在所述第一电极和第二电极之间的若干有机层，有机层中包括至少一层发光层，其特征在于，所述有机层中含有权利要求1～8中任一项所述的有机化合物。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022249505A1 (ja) * 2020-05-29 2022-12-01 株式会社Kyulux 化合物、発光材料および発光素子

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110407832A (zh) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 一种蒽醌类有机电致发光材料及其应用
CN110407825A (zh) * 2018-04-26 2019-11-05 北京鼎材科技有限公司 一种蒽醌类有机电致发光材料及其应用
CN109651406B (zh) * 2019-01-23 2021-01-08 苏州久显新材料有限公司 热激活延迟荧光化合物、发光材料及有机电致发光器件
CN112110873B (zh) * 2020-09-29 2022-08-26 信阳师范学院 氰基芳烃类聚集发光材料的合成及其应用
CN112409240A (zh) * 2020-11-20 2021-02-26 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
CN112409241B (zh) * 2020-11-27 2023-04-25 清华大学 一种有机化合物及其应用及采用该化合物的有机电致发光器
CN114656396A (zh) * 2020-12-22 2022-06-24 北京鼎材科技有限公司 一种有机化合物及其应用、包含其的有机电致发光器件
CN114685354A (zh) * 2020-12-28 2022-07-01 北京鼎材科技有限公司 一种有机化合物及其应用、包含其的有机电致发光器件
CN114685353A (zh) * 2020-12-28 2022-07-01 北京鼎材科技有限公司 用于有机发光器件的有机化合物、有机电致发光器件

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100171418A1 (en) * 2009-01-06 2010-07-08 Fujifilm Corporation Organic electroluminescent device
US20160268516A1 (en) * 2013-08-16 2016-09-15 Konica Minolta, Inc. Organic electroluminescent element, electronic device, light emitting device, and light emitting material
US20190181353A1 (en) * 2017-12-07 2019-06-13 Samsung Electronics Co., Ltd. Organic light-emitting device
CN110034243A (zh) * 2018-01-11 2019-07-19 北京鼎材科技有限公司 一种白光有机电致发光器件
CN110034234A (zh) * 2018-01-11 2019-07-19 北京鼎材科技有限公司 一种白光有机电致发光器件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100171418A1 (en) * 2009-01-06 2010-07-08 Fujifilm Corporation Organic electroluminescent device
US20160268516A1 (en) * 2013-08-16 2016-09-15 Konica Minolta, Inc. Organic electroluminescent element, electronic device, light emitting device, and light emitting material
US20190181353A1 (en) * 2017-12-07 2019-06-13 Samsung Electronics Co., Ltd. Organic light-emitting device
CN110034243A (zh) * 2018-01-11 2019-07-19 北京鼎材科技有限公司 一种白光有机电致发光器件
CN110034234A (zh) * 2018-01-11 2019-07-19 北京鼎材科技有限公司 一种白光有机电致发光器件

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022249505A1 (ja) * 2020-05-29 2022-12-01 株式会社Kyulux 化合物、発光材料および発光素子

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