WO2024031919A1 - Carbazole fused boron-nitrogen derivative, preparation method therefor, and use thereof - Google Patents

Carbazole fused boron-nitrogen derivative, preparation method therefor, and use thereof Download PDF

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WO2024031919A1
WO2024031919A1 PCT/CN2022/142170 CN2022142170W WO2024031919A1 WO 2024031919 A1 WO2024031919 A1 WO 2024031919A1 CN 2022142170 W CN2022142170 W CN 2022142170W WO 2024031919 A1 WO2024031919 A1 WO 2024031919A1
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formula
tert
compound
boron
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张晓宏
程迎春
王凯
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苏州大学
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09K2211/107—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms with other heteroatoms
    • 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
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms
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  • the invention belongs to the field of organic synthesis, and specifically relates to a carbazole-fused boron-nitrogen derivative and its preparation method and application.
  • Organic light-emitting diodes are widely used in flexible screen displays, daily lighting and other fields.
  • the current flexible OLED screens are mainly based on second-generation phosphorescent materials, and related technologies have long been monopolized by Japanese and Korean companies.
  • the current third generation of multiple resonance thermally activated delayed fluorescence (MR-TADF) materials is expected to develop organic light-emitting materials with higher color purity and reduction degree.
  • MR-TADF multiple resonance thermally activated delayed fluorescence
  • Related research will enhance future domestic high-definition and ultra-thin displays.
  • Technology plays an important role in breaking through the monopoly advantages of foreign related technologies.
  • thermally activated delayed fluorescent materials As the third generation of organic light-emitting materials, purely organic thermally activated delayed fluorescent materials have become a current research hotspot due to their low cost and high efficiency. In order to ensure an effective upconversion process that responds to intersystem crossing, thermally activated delayed fluorescent materials often achieve smaller ⁇ E ST s by designing twisted DA segments. However, this is easily avoidable and leads to an increase in molecular relaxation, which affects the device. color purity. Molecular design strategies based on multiple resonances proposed in recent years provide effective solutions for the development of devices with higher radiative transition rates, smaller half-peak widths, and higher color purity.
  • the current structure of the multiple resonance system mainly uses the DABNA-1 boron nitrogen system as the core, and the design of peripheral groups is used to control the luminescent materials with higher performance.
  • the current peripheral design is mainly based on the introduction of different non-fused push-pull electron groups, such as the classic tert-butylcarbazole boron nitrogen (BNCz) machine derivatives.
  • BNCz classic tert-butylcarbazole boron nitrogen
  • the light color of this type of material is mainly concentrated in blue. color to the green area.
  • MR-TADF luminescent materials involving orange-red light or red light range.
  • current MR-TADF materials also face problems such as serious concentration quenching, which seriously hinders their commercial application. Therefore, it will be a strategy full of great challenges to effectively achieve a large red shift of the spectrum through the expansion of peripheral conjugated structures and to design twisted molecular structures with concentration quenching effects.
  • the present invention provides a carbazole-fused boron-nitrogen derivative.
  • the carbazole-fused boron-nitrogen derivative is fused with one or two carbazole-fused boron-nitrogen derivatives based on the molecular structure of DABNA-1.
  • the chemical formula of carbazole, which can broaden the molecular conjugation, is as shown in formula A, formula B or formula C:
  • X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
  • R 1 is selected from hydrogen or tert-butyl
  • R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives .
  • the invention also provides a method for preparing the above-mentioned carbazole-fused boron-nitrogen derivative, which includes the following steps:
  • the chemical structure of compound I is selected from formula C, formula D or formula E; the chemical structure of compound II is formula F; the chemical structure of the first intermediate product is selected from formula G, formula H or formula J; Formula C, Formula D, Formula E, Formula F, Formula G, Formula H and Formula J are as follows:
  • X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
  • R 1 is selected from hydrogen or tert-butyl
  • R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives ;
  • the molar ratio of the organolithium reagent, compound III, compound IV and N,N-diisopropylethylamine is 1:1-5:1-5:1-5.
  • the organic solvent includes toluene, tetrahydrofuran, 1,4-dioxane or dimethyl sulfoxide solvent.
  • the base is sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate or cesium carbonate;
  • the palladium catalyst is Pd 2 (dba) 3 (tris(dibenzylideneacetone) dipalladium). ) or Pd(OAc) 2 (palladium acetate), purchased from Bide Pharmaceuticals.
  • step S1 the temperature of a reaction is 100-120°C and the time is 10-14h.
  • step S1 after adding the organic solvent, the nitrogen gas is replaced three times.
  • the organolithium reagent is tert-butyllithium or n-butyllithium.
  • the temperature of the secondary reaction is 50-70°C and the time is 2-3 hours.
  • the temperature of the three reactions is room temperature and the time is 1-2 h.
  • step S4 the temperature of the four reactions is 120-140°C and the time is 10-20 h.
  • the N,N-diisopropylethylamine adjusts pH.
  • the method for removing impurities is to add PBS aqueous solution to quench, extract with DCM (dichloromethane), dry, spin dry and then perform PE (petroleum ether) column chromatography.
  • the present invention also provides an organic electroluminescent device, including the above-mentioned carbazole-fused boron-nitrogen derivative.
  • the organic electroluminescent device includes a glass substrate, a hole transport layer, an electron blocking layer, a luminescent layer, an electron transport layer and a cathode layer; on the glass substrate, there is a hole transport layer formed by sequentially forming layers of organic compounds. layer, electron blocking layer, light-emitting layer and electron transport layer, and then form a cathode layer.
  • the present invention proposes a method for preparing a new type of carbazole-fused boron-nitrogen derivatives and applies it to organic electroluminescent devices, achieving excellent results.
  • This system expands the MR-TADF material molecule library, promotes the application of organic light-emitting diodes with high efficiency, high color purity and suppressed concentration quenching effect, and enables the design of thermally activated delayed fluorescent OLED materials closer to commercial needs in the future. Provides a certain foundation.
  • Figure 1 is a schematic diagram of the chemical formula of carbazole-fused boron-nitrogen derivatives.
  • Figure 2 is a schematic diagram of the chemical formulas of the raw materials and intermediate products for the synthesis of carbazole-fused boron-nitrogen derivatives.
  • Figure 3 is a schematic structural diagram of an organic electroluminescent device.
  • Example 2 As the preparation and performance evaluation of organic electroluminescent devices doped with fluorescent dyes
  • a glass plate with an ITO transparent electrode having a 3 mm wide indium tin oxide (ITO) film pattern in stripes was used as the substrate.
  • the surface was treated with ozone ultraviolet light.
  • Each layer was vacuum evaporated on the washed substrate using a vacuum evaporation method to produce an organic electroluminescent device with a light-emitting area of 9 mm2 as shown in the cross-sectional view in Figure 3.
  • the aforementioned glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1 ⁇ 10 -4 Pa. Then, on the glass substrate 1 shown in FIG. 1 , a hole transport layer 2 , an electron blocking layer 3 , a light emitting layer 4 and an electron transport layer 5 are sequentially formed as organic compound layers, and then a cathode layer 6 is formed.
  • TAPC 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline]
  • TCTA 4,4 was vacuum evaporated with a film thickness of 10 nm ',4"-tris(carbazol-9-yl)triphenylamine
  • mCP 1,3-di-9-carbazolylbenzene
  • the film is formed by heating.
  • the heated compound is vacuum evaporated at a film formation rate of 0.3-0.5nm.
  • a metal mask is arranged orthogonal to the ITO stripes to form a film cathode 6.
  • the cathode layer 6 is a film with a thickness of 1nm and 100nm respectively.
  • a two-layer structure formed by thick vacuum evaporation of lithium fluoride and aluminum.
  • Each film thickness is measured with a stylus type film thickness meter (DEKTAK).
  • the device is sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of 1 ppm or less. inside.
  • a glass sealing cover and the aforementioned film-forming substrate epoxy ultraviolet curable resin manufactured by Nagase ChemteX Corporation were used for sealing.
  • the boron-nitrogen derivative TCZ-F-DABNA with the fused structure of DABNA-1 carbazole can be efficiently synthesized, which can not only effectively achieve a large red shift of the spectrum, but also enhance the molecular stability to a certain extent. Twisting is beneficial to the preparation of optoelectronic devices with high efficiency, high color purity and resistance to concentration quenching.
  • the finally prepared device achieved orange-red light emission at 588nm and a maximum electroluminescence efficiency of 39.2% at 8wt% doping, and when the doping concentration was increased to 30wt%, the device still maintained more than 30% electroluminescence. efficiency.

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Abstract

The present invention belongs to the field of organic synthesis, and particularly relates to a carbazole fused boron-nitrogen derivative, a preparation method therefor, and the use thereof. The present invention provides the preparation method for the novel carbazole fused boron-nitrogen derivative and the use of same in high-efficiency organic electroluminescent devices. By means of ingenious route design, the boron-nitrogen derivative TCZ-F-DABNA having a DABNA-1-carbazole fused structure can be efficiently synthesized, which can effectively achieve a relatively large spectrum redshift and further enhance the distortion of molecules to a certain extent, thereby helping to manufacture optoelectronic devices having high efficiency, high color purity and concentration-quenching resistance. The system expands the MR-TADF material molecular library and promotes the application of organic light-emitting diodes having high efficiency, high color purity and concentration-quenching effect inhibition, thereby laying a certain foundation for designing in future thermally activated delayed fluorescence OLED materials that are more likely to meet the demand for commercialization.

Description

一种咔唑稠合的硼氮衍生物及其制备方法和应用A carbazole-fused boron-nitrogen derivative and its preparation method and application 技术领域Technical field
本发明属于有机合成领域，具体涉及一种咔唑稠合的硼氮衍生物及其制备方法和应用。The invention belongs to the field of organic synthesis, and specifically relates to a carbazole-fused boron-nitrogen derivative and its preparation method and application.
背景技术Background technique
有机发光二极管广泛应用于柔性屏显示，日常照明等领域，目前的柔性屏OLED屏主要是基于第二代磷光材料，且相关技术长期被日韩等公司垄断。当前的第三代的多重共振的热激活延迟荧光(MR-TADF)材料由于而有望开发具有更高色纯度和还原度的有机发光材料，相关研究将对增强未来国产的高清和超薄等显示技术，突破国外相关技术垄断优势起到重要的作用。Organic light-emitting diodes are widely used in flexible screen displays, daily lighting and other fields. The current flexible OLED screens are mainly based on second-generation phosphorescent materials, and related technologies have long been monopolized by Japanese and Korean companies. The current third generation of multiple resonance thermally activated delayed fluorescence (MR-TADF) materials is expected to develop organic light-emitting materials with higher color purity and reduction degree. Related research will enhance future domestic high-definition and ultra-thin displays. Technology plays an important role in breaking through the monopoly advantages of foreign related technologies.
作为第三代有机发光材料，纯有机的热活化延迟荧光材料因其成本低廉，效率高等优点而成为当前的研究热点。为了保证有效的反响系间窜越的上转化过程，热活化延迟荧光材料常通过设计扭曲的D-A片段以实现较小的ΔE STs，但是这容易避免的导致分子弛豫的增加，影响了器件的色纯度。近年来提出的基于多重共振的分子设计策略为开发具有较高的辐射跃迁速率，较小的半峰宽以及更高的色纯度的器件提供了有效的解决思路。经过多年研究，目前多重共振体系的结构主要是以DABNA-1硼氮体系为母核，通过外围等基团的设计调控出具有更高性能的发光材料。但是目前的外围设计主要是以引入不同的非稠合的推拉电子基团为主，例如经典的叔丁基咔唑硼氮(BNCz)机器衍生物，但是这类材料的光色主要集中在蓝色到绿色区域。目前涉及到橙红光或红光范围的MR-TADF发光材料还是极少。此外，目前的MR-TADF材料还面临着严重的浓度淬灭等问题，这严重阻碍了其商业化应用。因此通过外围共轭结构的扩展有效实现光谱的较大红移以及设计扭曲的具有浓度淬灭效应的分子结构将是一个充满巨大挑战的策略。 As the third generation of organic light-emitting materials, purely organic thermally activated delayed fluorescent materials have become a current research hotspot due to their low cost and high efficiency. In order to ensure an effective upconversion process that responds to intersystem crossing, thermally activated delayed fluorescent materials often achieve smaller ΔE ST s by designing twisted DA segments. However, this is easily avoidable and leads to an increase in molecular relaxation, which affects the device. color purity. Molecular design strategies based on multiple resonances proposed in recent years provide effective solutions for the development of devices with higher radiative transition rates, smaller half-peak widths, and higher color purity. After years of research, the current structure of the multiple resonance system mainly uses the DABNA-1 boron nitrogen system as the core, and the design of peripheral groups is used to control the luminescent materials with higher performance. However, the current peripheral design is mainly based on the introduction of different non-fused push-pull electron groups, such as the classic tert-butylcarbazole boron nitrogen (BNCz) machine derivatives. However, the light color of this type of material is mainly concentrated in blue. color to the green area. At present, there are still very few MR-TADF luminescent materials involving orange-red light or red light range. In addition, current MR-TADF materials also face problems such as serious concentration quenching, which seriously hinders their commercial application. Therefore, it will be a strategy full of great challenges to effectively achieve a large red shift of the spectrum through the expansion of peripheral conjugated structures and to design twisted molecular structures with concentration quenching effects.
发明内容Contents of the invention
为了解决上述存在的技术问题，本发明提供一种咔唑稠合的硼氮衍生物，所述咔唑稠合的硼氮衍生物是在DABNA-1分子结构的基础上稠合一个或两个能扩宽分子共轭的咔唑，其化学式如式A、式B或式C所示：In order to solve the above-mentioned technical problems, the present invention provides a carbazole-fused boron-nitrogen derivative. The carbazole-fused boron-nitrogen derivative is fused with one or two carbazole-fused boron-nitrogen derivatives based on the molecular structure of DABNA-1. The chemical formula of carbazole, which can broaden the molecular conjugation, is as shown in formula A, formula B or formula C:
Figure PCTCN2022142170-appb-000001
Figure PCTCN2022142170-appb-000001
其中，X选自氧、硫、硒、芴基或二苯基；Wherein, X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
R 1选自氢或叔丁基； R 1 is selected from hydrogen or tert-butyl;
R 2选自氢、氰基、甲基、叔丁基，二苯胺基，3,6-二叔丁基二苯胺基、2,6-(3,6-二叔丁基咔唑基)苯基、2,6-(3,6-二咔唑基)苯基、咔唑基、3,6-二叔丁基咔唑基、吩噻嗪基、吩噁嗪基或三嗪基衍生物。 R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives .
本发明还提供一种上述咔唑稠合的硼氮衍生物的制备方法，包括如下步骤：The invention also provides a method for preparing the above-mentioned carbazole-fused boron-nitrogen derivative, which includes the following steps:
S1：将化合物Ⅰ、化合物Ⅱ、碱和钯催化剂加入有机溶剂中，一次反应，得到第一中间产物(PhCltBuInPz)；所述化合物Ⅰ、化合物Ⅱ、碱和钯催化剂的摩尔比为1：1-3：2-12：0.04-0.1；S1: Add compound Ⅰ, compound Ⅱ, alkali and palladium catalyst into an organic solvent, and react in one time to obtain the first intermediate product (PhCltBuInPz); the molar ratio of compound Ⅰ, compound Ⅱ, alkali and palladium catalyst is 1:1- 3:2-12:0.04-0.1;
所述化合物Ⅰ的化学结构选自式C、式D或式E；所述化合物Ⅱ的化学结构为式F；所述第一中间产物的化学结构选自式G、式H或式J；所述式C、式D、式E、式F、式G、式H和式J如下所示：The chemical structure of compound I is selected from formula C, formula D or formula E; the chemical structure of compound II is formula F; the chemical structure of the first intermediate product is selected from formula G, formula H or formula J; Formula C, Formula D, Formula E, Formula F, Formula G, Formula H and Formula J are as follows:
Figure PCTCN2022142170-appb-000002
Figure PCTCN2022142170-appb-000002
其中，X选自氧、硫、硒、芴基或二苯基；Wherein, X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
R 1选自氢或叔丁基； R 1 is selected from hydrogen or tert-butyl;
R 2选自氢、氰基、甲基、叔丁基、二苯胺基、3,6-二叔丁基二苯胺基、2,6-(3,6-二叔丁基咔唑基)苯基、2,6-(3,6-二咔唑基)苯基、咔唑基、3,6-二叔丁基咔唑基、吩噻嗪基、吩噁嗪基或三嗪基衍生物； R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives ;
S2：将有机锂试剂、化合物Ⅲ和所述中间产物混合，二次反应后得到第二中间产物；所述化合物Ⅲ为叔丁基苯、间二甲苯或间三甲苯；S2: Mix the organolithium reagent, compound III and the intermediate product, and obtain the second intermediate product after the second reaction; the compound III is tert-butylbenzene, m-xylene or m-trimethylbenzene;
S3：向所述第二中间产物中加入化合物Ⅳ，三次反应后得到第三中间产物；所述化合物Ⅳ为三溴化硼或三碘化硼；S3: Add compound IV to the second intermediate product, and obtain the third intermediate product after three reactions; the compound IV is boron tribromide or boron triiodide;
S4：向所述第三中间产物中加入N,N-二异丙基乙胺，四次反应，除杂后得到所述咔唑稠合的硼氮衍生物；S4: Add N,N-diisopropylethylamine to the third intermediate product, react four times, and obtain the carbazole-fused boron nitrogen derivative after impurity removal;
所述有机锂试剂、化合物Ⅲ、化合物Ⅳ和N,N-二异丙基乙胺的摩尔比为1：1-5：1-5：1-5。The molar ratio of the organolithium reagent, compound III, compound IV and N,N-diisopropylethylamine is 1:1-5:1-5:1-5.
优选的，所述步骤S1中，有机溶剂包括甲苯、四氢呋喃、1，4-二氧六环或二甲亚砜溶剂。Preferably, in step S1, the organic solvent includes toluene, tetrahydrofuran, 1,4-dioxane or dimethyl sulfoxide solvent.
优选的，所述步骤S1中，碱为叔丁醇钠、叔丁醇钾、碳酸钠、碳酸钾或碳酸铯；钯催化剂为Pd 2(dba) 3(三(二亚苄基丙酮)二钯)或Pd(OAc) 2(醋酸钯)，购自毕得医药。 Preferably, in step S1, the base is sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate or cesium carbonate; the palladium catalyst is Pd 2 (dba) 3 (tris(dibenzylideneacetone) dipalladium). ) or Pd(OAc) 2 (palladium acetate), purchased from Bide Pharmaceuticals.
优选的，所述步骤S1中，一次反应的温度为100-120℃，时间为10-14h。Preferably, in step S1, the temperature of a reaction is 100-120°C and the time is 10-14h.
优选的，所述步骤S1中，加入有机溶剂后，抽换氮气三次。Preferably, in step S1, after adding the organic solvent, the nitrogen gas is replaced three times.
优选的，所述步骤S2中，有机锂试剂为叔丁基锂或正丁基锂。Preferably, in step S2, the organolithium reagent is tert-butyllithium or n-butyllithium.
优选的，所述步骤S2中，二次反应的温度为50-70℃，时间为2-3h。Preferably, in step S2, the temperature of the secondary reaction is 50-70°C and the time is 2-3 hours.
优选的，所述步骤S3中，三次反应的温度为室温，时间为1-2h。Preferably, in step S3, the temperature of the three reactions is room temperature and the time is 1-2 h.
优选的，所述步骤S4中，四次反应的温度为120-140℃，时间为10-20h。Preferably, in step S4, the temperature of the four reactions is 120-140°C and the time is 10-20 h.
所述N,N-二异丙基乙胺由于调节pH。The N,N-diisopropylethylamine adjusts pH.
优选的，所述步骤S4中，除杂的方法为加PBS水溶液淬灭，DCM(二氯甲烷)萃取，干燥，旋干后PE(石油醚)柱层析。Preferably, in step S4, the method for removing impurities is to add PBS aqueous solution to quench, extract with DCM (dichloromethane), dry, spin dry and then perform PE (petroleum ether) column chromatography.
本发明还提供一种有机电致发光器件，包括上述的咔唑稠合的硼氮衍生物。所述有机电致发光器件，包括玻璃基板、空穴传输层、电子阻挡层、发光层、电子传输层和阴极层；所述玻璃基板上，设有有机化合物层依次成膜形成的空穴传输层、电子阻挡层、发光层和电子传输层，然后成膜阴极层。The present invention also provides an organic electroluminescent device, including the above-mentioned carbazole-fused boron-nitrogen derivative. The organic electroluminescent device includes a glass substrate, a hole transport layer, an electron blocking layer, a luminescent layer, an electron transport layer and a cathode layer; on the glass substrate, there is a hole transport layer formed by sequentially forming layers of organic compounds. layer, electron blocking layer, light-emitting layer and electron transport layer, and then form a cathode layer.
本发明的技术方案相比现有技术具有以下优点：The technical solution of the present invention has the following advantages compared with the existing technology:
本发明提出了一类新型咔唑稠合的硼氮衍生物的制备方法，并将其应用于有机电致发光器件中，获得了极佳的效果。该体系扩展了MR-TADF材料分子库，推动了具有高效率、高色纯度以及具有抑制浓度淬灭效应的有机发光二极管的应用，为日后能设计更接近商业化需求的热活化延迟荧光OLED材料提供了一定的基础。The present invention proposes a method for preparing a new type of carbazole-fused boron-nitrogen derivatives and applies it to organic electroluminescent devices, achieving excellent results. This system expands the MR-TADF material molecule library, promotes the application of organic light-emitting diodes with high efficiency, high color purity and suppressed concentration quenching effect, and enables the design of thermally activated delayed fluorescent OLED materials closer to commercial needs in the future. Provides a certain foundation.
附图说明Description of drawings
图1为咔唑稠合的硼氮衍生物的化学式示意图。Figure 1 is a schematic diagram of the chemical formula of carbazole-fused boron-nitrogen derivatives.
图2为合成咔唑稠合的硼氮衍生物的原料和中间产物的化学式示意图。Figure 2 is a schematic diagram of the chemical formulas of the raw materials and intermediate products for the synthesis of carbazole-fused boron-nitrogen derivatives.
图3为有机电致发光器件的结构示意图。Figure 3 is a schematic structural diagram of an organic electroluminescent device.
附图标记说明：1-玻璃基板，2-空穴传输层，3-电子阻挡层，4-发光层，5-电子传输层，6-阴极层。Explanation of reference signs: 1-glass substrate, 2-hole transport layer, 3-electron blocking layer, 4-luminescent layer, 5-electron transport layer, 6-cathode layer.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。The present invention will be further described below in conjunction with the accompanying drawings and specific examples, so that those skilled in the art can better understand and implement the present invention, but the examples are not intended to limit the present invention.
实施例1Example 1
6,9,16,19-叔丁基-3b,10b,13b-三氮杂-20b-硼基芴[1,9-ab:1',9'-jk]苝(BNtBuInPz)的合成路线Synthetic route of 6,9,16,19-tert-butyl-3b,10b,13b-triaza-20b-borofluorene[1,9-ab:1',9'-jk]perylene (BNtBuInPz)
Figure PCTCN2022142170-appb-000003
Figure PCTCN2022142170-appb-000003
BNtBuInPz的合成路线Synthetic route of BNtBuInPz
Figure PCTCN2022142170-appb-000004
Figure PCTCN2022142170-appb-000004
①中间体tCzPhCltBuInPz：将原料1a(3.69g,10.0mmol)，tBuInPz(4.69g,10.0mmol)，Pd 2(dba) 3(275mg,0.30mmol)，叔丁醇钠(1.92g,20.0mmol)加入到250mL二口烧瓶中，置换N 2保护后，加入甲苯(100mL)，继续抽换氮气三次后，加入四氟硼酸三叔丁基膦(580mg,2.0mmol)，110℃回流反应12h，TLC显示原料1a消失，加水淬灭，DCM萃取，干燥，旋干，PE:DCM＝10:1柱层析，得黄色固体PhCltBuInPz(5.45g,72％)。 ①Intermediate tCzPhCltBuInPz: Add raw materials 1a (3.69g, 10.0mmol), tBuInPz (4.69g, 10.0mmol), Pd 2 (dba) 3 (275mg, 0.30mmol), and sodium tert-butoxide (1.92g, 20.0mmol). Into a 250mL two-necked flask, after replacing N2 protection, add toluene (100mL), continue to replace nitrogen three times, add tri-tert-butylphosphine tetrafluoroborate (580mg, 2.0mmol), reflux at 110°C for 12h, TLC shows The raw material 1a disappeared, quenched with water, extracted with DCM, dried, spun to dryness, and subjected to PE:DCM=10:1 column chromatography to obtain yellow solid PhCltBuInPz (5.45g, 72%).
产物表征： 1H NMR(400MHz,CD 2Cl 2):δ8.08(d,J＝1.9Hz,2H),7.93(s,1H),7.85–7.37(m,8H),7.36–7.32(m,1H),7.04(d,J＝8.5Hz,1H),6.93(dd,J＝8.7,2.4Hz,1H),6.70(d,J＝37.7Hz,2H),6.03(d,J＝7.9Hz,1H),5.69(s,1H),1.37–1.34(m,27H),1.21(s,9H). 13C NMR(101MHz,CD 2Cl 2):δ146.49,143.38,143.33,139.23,139.10,138.68,131.35,130.13,123.89, 123.76,123.46,123.40,116.57,114.19,113.89,109.40,109.22,103.30,34.84,34.72,34.69,31.80,31.69,31.48.MALDI-TOF:Calculated:755.401,Found:755.65. Product characterization: 1 H NMR (400MHz, CD 2 Cl 2 ): δ8.08 (d, J＝1.9Hz, 2H), 7.93 (s, 1H), 7.85–7.37 (m, 8H), 7.36–7.32 (m ,1H),7.04(d,J＝8.5Hz,1H),6.93(dd,J＝8.7,2.4Hz,1H),6.70(d,J＝37.7Hz,2H),6.03(d,J＝7.9Hz ,1H),5.69(s,1H),1.37–1.34(m,27H),1.21(s,9H). 13 C NMR (101MHz, CD 2 Cl 2 ): δ146.49,143.38,143.33,139.23,139.10,138.68 ,131.35,130.13,123.89, 123.76,123.46,123.40,116.57,114.19,113.89,109.40,109.22,103.30,34.84,34.72,34.69,31.80,31.69,31.48.M ALDI-TOF:Calculated:755.401,Found:755.65.
Figure PCTCN2022142170-appb-000005
Figure PCTCN2022142170-appb-000005
②将原料tCzPhCltBuInPz(7.56g,10.0mmol)加入到100mL二口烧瓶中，置换N 2保护后，加入无水叔丁基苯(30mL)，抽换氮气三次后，于-40℃低温下加入叔丁基锂(1.3mol/L in pentane,19.0mL,25.0mmol)，移走低温浴，60℃反应2h。-40℃下缓慢加入三溴化硼(2.40mL,25.0mmol)，室温反应1h。冰浴下加入N,N-二异丙基乙胺(3.50mL,25.0mmol)，130℃反应过夜。取样TLC显示原料PhCltBuInPz消失，有新点生成，加PBS水溶液淬灭，DCM萃取，干燥，旋干，PE柱层析，得黄色固体BNtBuInPz(5.69mg,78％)。 ② Add the raw material tCzPhCltBuInPz (7.56g, 10.0mmol) into a 100mL two-necked flask. After replacing the N2 protection, add anhydrous tert-butylbenzene (30mL). After exchanging nitrogen three times, add tert-butylbenzene (30mL) at a low temperature of -40°C. Butyllithium (1.3mol/L in pentane, 19.0mL, 25.0mmol), remove the low temperature bath, and react at 60°C for 2 hours. Boron tribromide (2.40 mL, 25.0 mmol) was slowly added at -40°C, and the reaction was carried out at room temperature for 1 hour. Add N,N-diisopropylethylamine (3.50 mL, 25.0 mmol) under ice bath, and react at 130°C overnight. Sampling TLC showed that the raw material PhCltBuInPz disappeared and new spots were generated. Add PBS aqueous solution to quench, extract with DCM, dry, spin dry, and perform PE column chromatography to obtain yellow solid BNtBuInPz (5.69 mg, 78%).
产物表征： 1H NMR(400MHz,CD 2Cl 2):δ8.80(d,J＝1.9Hz,1H),8.53(d,J＝1.9Hz,1H),8.36(d,J＝8.8Hz,1H),8.32(d,J＝2.0Hz,1H),8.26(s,1H),8.14(d,J＝2.0Hz,3H),7.96(s,1H),7.90(d,J＝7.7Hz,1H),7.80(s,1H),7.75–7.66(m,3H),7.66–7.61(m,1H),7.33(s,1H),1.68(s,9H),1.57(s,9H),1.52(s,9H),1.46(s,9H). 13C NMR(101MHz,CD 2Cl 2):δ146.15,145.28,144.81,144.62,142.51,141.72,138.13,137.23,132.84,129.32,128.43,126.87,126.45,124.41,124.04,123.48,123.27,123.03,120.62,117.46,117.24,114.09,113.91,113.81,112.01,35.18,35.08,34.70,34.67,34.62,34.56,31.93,31.61,31.59,31.55,29.04,26.92,25.24,20.41,19.18,11.18.MALDI-TOF:Calculated:729.425,Found:729.649. Product characterization: 1 H NMR (400MHz, CD 2 Cl 2 ): δ8.80 (d, J = 1.9 Hz, 1H), 8.53 (d, J = 1.9 Hz, 1H), 8.36 (d, J = 8.8 Hz, 1H),8.32(d,J＝2.0Hz,1H),8.26(s,1H),8.14(d,J＝2.0Hz,3H),7.96(s,1H),7.90(d,J＝7.7Hz, 1H),7.80(s,1H),7.75–7.66(m,3H),7.66–7.61(m,1H),7.33(s,1H),1.68(s,9H),1.57(s,9H),1.52 (s,9H),1.46(s,9H). 13 C NMR (101MHz, CD 2 Cl 2 ): δ146.15,145.28,144.81,144.62,142.51,141.72,138.13,137.23,132.84,129.32,128.43,126.87,1 26.45 ,124.41,124.04,123.48,123.27,123.03,120.62,117.46,117.24,114.09,113.91,113.81,112.01,35.18,35.08,34.70,34.67,34.62,34.56,31 .93,31.61,31.59,31.55,29.04,26.92,25.24 ,20.41,19.18,11.18.MALDI-TOF:Calculated:729.425,Found:729.649.
实施例2Example 2
TCZ-F-DABNA的合成路线Synthetic route of TCZ-F-DABNA
Figure PCTCN2022142170-appb-000006
Figure PCTCN2022142170-appb-000006
①中间体PhCltBuInPz：将原料2a(1.75g,6.0mmol)，tBuInPz(5.75g,15.6mmol)，Pd 2(dba) 3(357mg,0.39mmol)，叔丁醇钠(2.50g,26.0mmol)加入到250mL二口烧瓶中，置换N 2保护后，加入甲苯(100mL)，继续抽换氮气三次后，加入四氟硼酸三叔丁基膦(1.13g,3.90mmol)，110℃回流反应12h，TLC显示原料2-氯-1,3-二溴苯消失，加水淬灭，DCM 萃取，干燥，旋干，PE:DCM＝10:1柱层析，得黄色固体PhCltBuInPz(3.92g,71％)。 ①Intermediate PhCltBuInPz: Add raw materials 2a (1.75g, 6.0mmol), tBuInPz (5.75g, 15.6mmol), Pd 2 (dba) 3 (357mg, 0.39mmol), and sodium tert-butoxide (2.50g, 26.0mmol). Into a 250mL two-necked flask, after replacing N2 protection, add toluene (100mL), continue to replace nitrogen three times, add tri-tert-butylphosphine tetrafluoroborate (1.13g, 3.90mmol), reflux at 110°C for 12h, and perform TLC It shows that the raw material 2-chloro-1,3-dibromobenzene has disappeared, quenched by adding water, extracted with DCM, dried, spin-dried, and subjected to PE:DCM=10:1 column chromatography to obtain yellow solid PhCltBuInPz (3.92g, 71%).
产物表征： 1H NMR(400MHz,CD 2Cl 2): 1H NMR(400MHz,CD 2Cl 2):δ7.93(d,J＝1.9Hz,2H),7.75(ddd,J＝9.2,6.7,4.2Hz,3H),7.67(t,J＝8.4Hz,2H),7.53(dd,J＝8.0,1.5Hz,2H),7.46(dd,J＝8.9,2.0Hz,2H),7.16(s,2H),6.74(t,J＝7.7Hz,2H),6.60(dt,J＝15.9,7.8Hz,2H),5.97–5.59(m,4H),1.35(s,18H),1.17(s,18H). 13C NMR(101MHz,CD 2Cl 2):δ146.46,146.40,143.33,139.14,135.53,134.10,131.70,130.30,129.39,123.66,121.93,121.88,121.42,117.10,114.18,113.71,113.58,111.95,103.31,103.23,34.77,34.59,31.63,31.57,31.38.MALDI-TOF:Calculated:844.427,Found:844.682. Product characterization: 1 H NMR (400MHz, CD 2 Cl 2 ): 1 H NMR (400MHz, CD 2 Cl 2 ): δ7.93 (d, J = 1.9 Hz, 2H), 7.75 (ddd, J = 9.2, 6.7 ,4.2Hz,3H),7.67(t,J＝8.4Hz,2H),7.53(dd,J＝8.0,1.5Hz,2H),7.46(dd,J＝8.9,2.0Hz,2H),7.16(s ,2H),6.74(t,J＝7.7Hz,2H),6.60(dt,J＝15.9,7.8Hz,2H),5.97–5.59(m,4H),1.35(s,18H),1.17(s, 18H). 13 C NMR (101MHz, CD 2 Cl 2 ): δ146.46,146.40,143.33,139.14,135.53,134.10,131.70,130.30,129.39,123.66,121.93,121.88,121.42,117.10 ,114.18,113.71,113.58,111.95 ,103.31,103.23,34.77,34.59,31.63,31.57,31.38.MALDI-TOF:Calculated:844.427,Found:844.682.
Figure PCTCN2022142170-appb-000007
Figure PCTCN2022142170-appb-000007
②将原料PhCltBuInPz(1.20g,1.42mmol)加入到100mL二口烧瓶中，置换N 2保护后，加入无水叔丁基苯(30mL)，抽换氮气三次后，于-40℃低温下加入叔丁基锂(1.3mol/L in pentane,2.75mL,3.55mmol)，移走低温浴，60℃反应2h。-40℃下缓慢加入三溴化硼(0.34mL,3.50mmol)，室温反应1h。冰浴下加入N,N-二异丙基乙胺(0.56mL,3.50mmol)，130℃反应过夜。取样TLC显示原料PhCltBuInPz消失，有新点生成，加PBS水溶液淬灭，DCM萃取，干燥，旋干，PE柱层析，得黄色固体BNtBuInPz(954mg,82％)。 ② Add the raw material PhCltBuInPz (1.20g, 1.42mmol) into a 100mL two-necked flask. After replacing the N2 protection, add anhydrous tert-butylbenzene (30mL). After exchanging nitrogen three times, add tert-butylbenzene (30mL) at a low temperature of -40°C. Butyllithium (1.3mol/L in pentane, 2.75mL, 3.55mmol), remove the low temperature bath, and react at 60°C for 2 hours. Boron tribromide (0.34 mL, 3.50 mmol) was slowly added at -40°C, and the reaction was carried out at room temperature for 1 hour. Add N,N-diisopropylethylamine (0.56 mL, 3.50 mmol) under ice bath, and react at 130°C overnight. Sampling TLC showed that the raw material PhCltBuInPz disappeared and new spots were generated. Add PBS aqueous solution to quench, extract with DCM, dry, spin dry, and perform PE column chromatography to obtain yellow solid BNtBuInPz (954 mg, 82%).
产物表征： 1H NMR(400MHz,CDCl 3):δ8.11(d,J＝1.9Hz,2H),7.88(dd,J＝35.5,8.1Hz,8H),7.72(s,4H),7.62–7.48(m,3H),7.17(s,2H),1.49(s,18H),1.45(s,18H). 13C NMR(101MHz,CDCl 3):δ146.08,144.47,134.47,132.89,128.07,127.58,126.57,123.95,123.28,122.92,117.42,114.19,113.91,111.91,35.32,34.81,31.96,31.90,31.78,29.73.MALDI-TOF:Calculated:818.452,Found:818.697. Product characterization: 1 H NMR (400MHz, CDCl 3 ): δ8.11(d,J＝1.9Hz,2H),7.88(dd,J＝35.5,8.1Hz,8H),7.72(s,4H),7.62– 7.48(m,3H),7.17(s,2H),1.49(s,18H),1.45(s,18H). 13 C NMR (101MHz, CDCl 3 ): δ146.08,144.47,134.47,132.89,128.07,127.58, 126.57,123.95,123.28,122.92,117.42,114.19,113.91,111.91,35.32,34.81,31.96,31.90,31.78,29.73.MALDI-TOF:Calculated:818.452,Found:818.697.
实施例3Example 3
以实施例2为荧光掺杂染料的有机电致发光器件的制作与性能评价Using Example 2 as the preparation and performance evaluation of organic electroluminescent devices doped with fluorescent dyes
使用3mm宽的氧化铟锡(ITO)膜图案的成条纹状的、带有ITO透明电极的玻璃板作为基板。用异丙醇将玻璃基板洗涤后，通过臭氧紫外线进行表面处理。在洗涤后的基板上用真空蒸镀法进行各层的真空蒸镀，制作剖面图如图3所示的发光面积9mm 2的有机电致发光器件。 A glass plate with an ITO transparent electrode having a 3 mm wide indium tin oxide (ITO) film pattern in stripes was used as the substrate. After the glass substrate was washed with isopropyl alcohol, the surface was treated with ozone ultraviolet light. Each layer was vacuum evaporated on the washed substrate using a vacuum evaporation method to produce an organic electroluminescent device with a light-emitting area of 9 mm2 as shown in the cross-sectional view in Figure 3.
首先，将前述玻璃基板导入真空蒸镀槽内，减压至1×10 -4Pa。然后在图1中所示的玻璃基板1上，作为有机化合物层依次成膜成空穴传输层2、电子阻挡层3、发光层4和电子传输层5，然后成膜阴极层6。以30nm厚的膜厚真空蒸镀的4,4'-环己基二[N,N-二(4-甲基苯基)苯胺](TAPC)和10nm厚的膜厚真空蒸镀的4,4',4”-三(咔唑-9-基)三苯胺(TCTA)作为空穴传输层2，以10nm厚的膜厚真空蒸镀的1,3-二-9-咔唑基苯(mCP)为电子阻挡层3，以20nm厚的膜厚真空蒸镀比例为92：8(质量％)的9-(2-(9-苯基-9H-咔唑-3-基)苯基)-9H-3,9'-联咔唑(PhCzBCz)与本发明实施例2中合成的产物作为发光层4，以40nm厚的膜厚真空蒸镀的3,3'-[5'-[3-(3-吡啶基)苯基][1,1':3',1”-三联苯]-3,3”-二基]二吡啶(TmPyPb)作为电子传输层5。其中各个有机材料通过电阻加热方式成膜。加热化合物以0.3-0.5nm的成膜速率真空蒸镀。最后以与ITO条纹正交的方式配置金属掩膜，构成膜阴极6。阴极层6是分别以1nm和100nm的膜厚真空蒸镀氟化锂和铝而形成的两层结构。各个膜厚用触针式膜厚测定器(DEKTAK)测定。进而，将器件密封在水和氧分浓度1ppm以下的氮气氛手套箱内。密封使用玻璃质的密封盖和前述成膜基板环氧性紫外线固化树脂(Nagase ChemteX Corporation制造)。 First, the aforementioned glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1×10 -4 Pa. Then, on the glass substrate 1 shown in FIG. 1 , a hole transport layer 2 , an electron blocking layer 3 , a light emitting layer 4 and an electron transport layer 5 are sequentially formed as organic compound layers, and then a cathode layer 6 is formed. 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) was vacuum evaporated with a film thickness of 30 nm and 4,4 was vacuum evaporated with a film thickness of 10 nm ',4"-tris(carbazol-9-yl)triphenylamine (TCTA) was used as the hole transport layer 2, and 1,3-di-9-carbazolylbenzene (mCP) was vacuum evaporated with a film thickness of 10 nm. ) is the electron blocking layer 3, and 9-(2-(9-phenyl-9H-carbazol-3-yl)phenyl)- is vacuum evaporated with a film thickness of 20 nm in a ratio of 92:8 (mass %) 9H-3,9'-bicarbazole (PhCzBCz) and the product synthesized in Example 2 of the present invention were used as the light-emitting layer 4, and 3,3'-[5'-[3- was vacuum evaporated with a film thickness of 40 nm (3-Pyridyl)phenyl][1,1':3',1"-terphenyl]-3,3"-diyl]dipyridine (TmPyPb) serves as the electron transport layer 5. Each organic material passes through a resistor The film is formed by heating. The heated compound is vacuum evaporated at a film formation rate of 0.3-0.5nm. Finally, a metal mask is arranged orthogonal to the ITO stripes to form a film cathode 6. The cathode layer 6 is a film with a thickness of 1nm and 100nm respectively. A two-layer structure formed by thick vacuum evaporation of lithium fluoride and aluminum. Each film thickness is measured with a stylus type film thickness meter (DEKTAK). Furthermore, the device is sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of 1 ppm or less. inside. A glass sealing cover and the aforementioned film-forming substrate epoxy ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used for sealing.
对所制备的有机电致发光器件施加直流电流，使用Spectrascan PR650亮度计来评价发光性能，使用电脑控制的Keithley 2400数字源表测量电流-电压特性。作为发光特性，测定在随外加直流电压变化下的CIE色坐标值、最大亮度(cd/m 2)、外量子效率(％)、功率效率(lm/W)。所制作的器件的测定值为(0.54,0.44)，12740cd/m 2，39.2％和108.1lm/W。且在30wt％的高掺杂浓度下器件仍然实现了30.3％的EQE(外量子效率)。 DC current was applied to the prepared organic electroluminescent device, the luminescence performance was evaluated using a Spectrascan PR650 luminance meter, and the current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter. As the luminescence characteristics, the CIE color coordinate value, maximum brightness (cd/m 2 ), external quantum efficiency (%), and power efficiency (lm/W) with changes in applied DC voltage were measured. The measured values of the fabricated device were (0.54, 0.44), 12740cd/m 2 , 39.2% and 108.1lm/W. And at a high doping concentration of 30wt%, the device still achieved an EQE (external quantum efficiency) of 30.3%.
效果评价1 Effect evaluation 1
为了设计出具有较高效率、高色纯度以及能够在一定程度上抑制浓度淬灭的具有商业化应用潜力的优秀器件，基于DABNA-1母核体系优良的光电性能，结合稠合咔唑在不明显影响MR效应的前提下具有扩宽分子共轭作用，且外围稠合结构在较大程度上增大了分子结构的扭曲的效果。提出了一种新型咔唑稠合的硼氮衍生物的制备方法及其在高效有机电致发光器件中的应用。通过巧妙的路线设计，可以高效合成具有DABNA-1咔唑的稠合结构的硼氮衍生物TCZ-F-DABNA，不仅可以有效地实现光谱的较大红移，且能在一定程度上增强分子的扭曲，有利于制备高效，高色纯度且具有抗浓度淬灭的光电器件。结果表明，TCZ-F-DABNA中咔唑的引入不仅增强扩宽了分子的共轭结构，同时保证了器件较小的半峰宽(FWHM＝62nm)。最终制备的器件在8wt％的掺杂下实现了588nm的橙红光发光以及最大39.2％的电致发光效率，且当掺杂浓度提升到30wt％时，器件仍然保持了超过30％的电致发光效率。In order to design excellent devices with high efficiency, high color purity and the ability to suppress concentration quenching to a certain extent with commercial application potential, based on the excellent photoelectric properties of the DABNA-1 core system, combined with fused carbazole, On the premise of significantly affecting the MR effect, it has the effect of broadening the molecular conjugation, and the peripheral fused structure increases the distortion of the molecular structure to a large extent. The preparation method of a new carbazole-fused boron-nitrogen derivative and its application in high-efficiency organic electroluminescent devices are proposed. Through ingenious route design, the boron-nitrogen derivative TCZ-F-DABNA with the fused structure of DABNA-1 carbazole can be efficiently synthesized, which can not only effectively achieve a large red shift of the spectrum, but also enhance the molecular stability to a certain extent. Twisting is beneficial to the preparation of optoelectronic devices with high efficiency, high color purity and resistance to concentration quenching. The results show that the introduction of carbazole into TCZ-F-DABNA not only enhances and broadens the conjugated structure of the molecule, but also ensures a smaller half-peak width of the device (FWHM=62nm). The finally prepared device achieved orange-red light emission at 588nm and a maximum electroluminescence efficiency of 39.2% at 8wt% doping, and when the doping concentration was increased to 30wt%, the device still maintained more than 30% electroluminescence. efficiency.
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Obviously, the above-mentioned embodiments are only examples for clear explanation and are not intended to limit the implementation. For those of ordinary skill in the art, other changes or modifications may be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. The obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims (10)

  1. 一种咔唑稠合的硼氮衍生物，其特征在于，所述咔唑稠合的硼氮衍生物是在DABNA-1分子结构的基础上稠合一个或两个能扩宽分子共轭的咔唑，其化学式如式A、式B或式C所示：A carbazole-fused boron-nitrogen derivative, characterized in that the carbazole-fused boron-nitrogen derivative is based on the molecular structure of DABNA-1 and is fused with one or two compounds that can broaden the molecular conjugation. Carbazole, its chemical formula is as shown in Formula A, Formula B or Formula C:
    Figure PCTCN2022142170-appb-100001
    Figure PCTCN2022142170-appb-100001
    其中，X选自氧、硫、硒、芴基或二苯基；Wherein, X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
    R 1选自氢或叔丁基； R 1 is selected from hydrogen or tert-butyl;
    R 2选自氢、氰基、甲基、叔丁基，二苯胺基，3,6-二叔丁基二苯胺基、2,6-(3,6-二叔丁基咔唑基)苯基、2,6-(3,6-二咔唑基)苯基、咔唑基、3,6-二叔丁基咔唑基、吩噻嗪基、吩噁嗪基或三嗪基衍生物。 R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives .
  2. 一种权利要求1所述咔唑稠合的硼氮衍生物的制备方法，其特征在于，包括如下步骤：A method for preparing carbazole-fused boron-nitrogen derivatives according to claim 1, characterized in that it includes the following steps:
    S1：将化合物Ⅰ、化合物Ⅱ、碱和钯催化剂加入有机溶剂中，一次反应，得到第一中间产物；所述化合物Ⅰ、化合物Ⅱ、碱和钯催化剂的摩尔比为1：1-3：2-12：0.04-0.1；S1: Add compound Ⅰ, compound Ⅱ, alkali and palladium catalyst into an organic solvent and react in one time to obtain the first intermediate product; the molar ratio of compound Ⅰ, compound Ⅱ, alkali and palladium catalyst is 1:1-3:2 -12:0.04-0.1;
    所述化合物Ⅰ的化学结构选自式C、式D或式E；所述化合物Ⅱ的化学结构为式F；所述第一中间产物的化学结构选自式G、式H或式J；所述式C、式D、式E、式F、式G、式H和式J如下所示：The chemical structure of compound I is selected from formula C, formula D or formula E; the chemical structure of compound II is formula F; the chemical structure of the first intermediate product is selected from formula G, formula H or formula J; Formula C, Formula D, Formula E, Formula F, Formula G, Formula H and Formula J are as follows:
    Figure PCTCN2022142170-appb-100002
    Figure PCTCN2022142170-appb-100002
    其中，X选自氧、硫、硒、芴基或二苯基；Wherein, X is selected from oxygen, sulfur, selenium, fluorenyl or diphenyl;
    R 1选自氢或叔丁基； R 1 is selected from hydrogen or tert-butyl;
    R 2选自氢、氰基、甲基、叔丁基、二苯胺基、3,6-二叔丁基二苯胺基、2,6-(3,6-二叔丁基咔唑基)苯基、2,6-(3,6-二咔唑基)苯基、咔唑基、3,6-二叔丁基咔唑基、吩噻嗪基、吩噁嗪基或三嗪基衍生物； R 2 is selected from hydrogen, cyano, methyl, tert-butyl, diphenylamine, 3,6-di-tert-butyldiphenylamine, 2,6-(3,6-di-tert-butylcarbazolyl)benzene base, 2,6-(3,6-dicarbazolyl)phenyl, carbazolyl, 3,6-di-tert-butylcarbazolyl, phenothiazinyl, phenoxazinyl or triazinyl derivatives ;
    S2：将有机锂试剂、化合物Ⅲ和所述中间产物混合，二次反应后得到第二中间产物；所述化合物Ⅲ为叔丁基苯、间二甲苯或间三甲苯；S2: Mix the organolithium reagent, compound III and the intermediate product, and obtain the second intermediate product after the second reaction; the compound III is tert-butylbenzene, m-xylene or m-trimethylbenzene;
    S3：向所述第二中间产物中加入化合物Ⅳ，三次反应后得到第三中间产物；所述化合物Ⅳ为三溴化硼或三碘化硼；S3: Add compound IV to the second intermediate product, and obtain the third intermediate product after three reactions; the compound IV is boron tribromide or boron triiodide;
    S4：向所述第三中间产物中加入N,N-二异丙基乙胺，四次反应，除杂后得到所述咔唑稠合的硼氮衍生物；S4: Add N,N-diisopropylethylamine to the third intermediate product, react four times, and obtain the carbazole-fused boron nitrogen derivative after impurity removal;
    所述有机锂试剂、化合物Ⅲ、化合物Ⅳ和N,N-二异丙基乙胺的摩尔比为1：1-5：1-5：1-5。The molar ratio of the organolithium reagent, compound III, compound IV and N,N-diisopropylethylamine is 1:1-5:1-5:1-5.
  3. 如权利要求2所述的制备方法，其特征在于，所述步骤S1中，有机溶剂包括甲苯、四氢呋喃、1，4-二氧六环或二甲亚砜溶剂。The preparation method of claim 2, wherein in step S1, the organic solvent includes toluene, tetrahydrofuran, 1,4-dioxane or dimethyl sulfoxide solvent.
  4. 如权利要求2所述的制备方法，其特征在于，所述步骤S1中，碱为叔丁醇钠、叔丁醇钾、碳酸钠、碳酸钾或碳酸铯；钯催化剂为三(二亚苄基丙酮)二钯或醋酸钯。The preparation method according to claim 2, wherein in step S1, the base is sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate or cesium carbonate; the palladium catalyst is tris(dibenzylidene) acetone) dipalladium or palladium acetate.
  5. 如权利要求2所述的制备方法，其特征在于，所述步骤S1中，一次反应的温度为100-120℃，时间为10-14h。The preparation method according to claim 2, characterized in that in step S1, the temperature of one reaction is 100-120°C and the time is 10-14h.
  6. 如权利要求2所述的制备方法，其特征在于，所述步骤S2中，有机锂试剂为叔丁基锂或正丁基锂。The preparation method of claim 2, wherein in step S2, the organolithium reagent is tert-butyllithium or n-butyllithium.
  7. 如权利要求2所述的制备方法，其特征在于，所述步骤S2中，二次反应的温度为50-70℃，时间为2-3h。The preparation method according to claim 2, characterized in that in step S2, the temperature of the secondary reaction is 50-70°C and the time is 2-3h.
  8. 如权利要求2所述的制备方法，其特征在于，所述步骤S3中，三次反应的温度为室温，时间为1-2h。The preparation method according to claim 2, characterized in that in step S3, the temperature of the three reactions is room temperature and the time is 1-2 h.
  9. 如权利要求2所述的制备方法，其特征在于，所述步骤S4中，四次反应的温度为120-140℃，时间为10-20h。The preparation method according to claim 2, characterized in that in step S4, the temperature of the four reactions is 120-140°C and the time is 10-20h.
  10. 一种有机电致发光器件，其特征在于，包括权利要求1所述的咔唑稠合的硼氮衍生物。An organic electroluminescent device, characterized by comprising the carbazole-fused boron-nitrogen derivative according to claim 1.
PCT/CN2022/142170 2022-08-12 2022-12-27 Carbazole fused boron-nitrogen derivative, preparation method therefor, and use thereof WO2024031919A1 (en)

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