WO2024031919A1 - Dérivé de bore-azote fusionné au carbazole, son procédé de préparation et son utilisation - Google Patents

Dérivé de bore-azote fusionné au carbazole, son procédé de préparation et son utilisation 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
preparation
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PCT/CN2022/142170
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Chinese (zh)
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张晓宏
程迎春
王凯
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苏州大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention appartient au domaine de la synthèse organique, et concerne en particulier un dérivé de bore-azote fusionné au carbazole, son procédé de préparation et son utilisation. La présente invention concerne le procédé de préparation du nouveau dérivé de bore-azote fusionné au carbazole et son utilisation dans des dispositifs électroluminescents organiques à haut rendement. Une conception de voie ingénieuse est utilisée pour synthétiser de manière efficace le dérivé de bore-azote TCZ-F-DABNA ayant une structure fusionnée d'ADN-1-carbazole, ce qui permet d'obtenir efficacement un décalage de spectre relativement grand et d'améliorer davantage la distorsion de molécules dans une certaine mesure, ce qui permet de fabriquer des dispositifs optoélectroniques ayant une efficacité élevée, une pureté de couleur élevée et une résistance à l'extinction de haute concentration. Le système étend la bibliothèque moléculaire de matériau MR-TADF et favorise l'application de diodes électroluminescentes organiques ayant une efficacité élevée, une pureté de couleur élevée et une inhibition d'effet de désactivation de concentration, ce qui permet de poser une certaine fondation pour concevoir dans le futurs des matériaux OLED à fluorescence retardée activés thermiquement qui sont plus susceptibles de satisfaire la demande commerciale.
PCT/CN2022/142170 2022-08-12 2022-12-27 Dérivé de bore-azote fusionné au carbazole, son procédé de préparation et son utilisation WO2024031919A1 (fr)

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CN202210969389.5 2022-08-12
CN202210969389.5A CN115433217B (zh) 2022-08-12 2022-08-12 一种咔唑稠合的硼氮衍生物及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
CN115433217B (zh) * 2022-08-12 2023-08-25 苏州大学 一种咔唑稠合的硼氮衍生物及其制备方法和应用

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CN114106026A (zh) * 2021-11-05 2022-03-01 东华理工大学 一种双硼有机发光材料及发光器件应用
CN114106028A (zh) * 2021-12-10 2022-03-01 华中科技大学 一种吲哚并咔唑双硼衍生物、其制备和应用
CN114149458A (zh) * 2021-11-29 2022-03-08 苏州大学 一种b/n类有机电致发光材料及其制备方法与应用
KR20220048445A (ko) * 2020-10-12 2022-04-19 에스에프씨 주식회사 보론 함유 다환 고리 화합물 및 이를 이용한 유기발광소자
CN114773366A (zh) * 2022-03-22 2022-07-22 苏州大学 一种羰基稠合的硼氮衍生物及其制备方法和应用
CN115433217A (zh) * 2022-08-12 2022-12-06 苏州大学 一种羰基稠合的硼氮衍生物及其制备方法和应用

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Publication number Priority date Publication date Assignee Title
CN108794494A (zh) * 2018-06-18 2018-11-13 南京邮电大学 一种三并咔唑-芳香胺衍生物空穴传输材料及其制备方法与应用
CN110790782A (zh) * 2019-11-11 2020-02-14 北京大学深圳研究生院 一种深蓝色有机发光材料及其制备方法与应用
CN112940023A (zh) * 2019-12-11 2021-06-11 北京鼎材科技有限公司 一种有机化合物及应用以及采用其的有机电致发光器件
KR20220048445A (ko) * 2020-10-12 2022-04-19 에스에프씨 주식회사 보론 함유 다환 고리 화합물 및 이를 이용한 유기발광소자
CN114106026A (zh) * 2021-11-05 2022-03-01 东华理工大学 一种双硼有机发光材料及发光器件应用
CN114149458A (zh) * 2021-11-29 2022-03-08 苏州大学 一种b/n类有机电致发光材料及其制备方法与应用
CN114106028A (zh) * 2021-12-10 2022-03-01 华中科技大学 一种吲哚并咔唑双硼衍生物、其制备和应用
CN114773366A (zh) * 2022-03-22 2022-07-22 苏州大学 一种羰基稠合的硼氮衍生物及其制备方法和应用
CN115433217A (zh) * 2022-08-12 2022-12-06 苏州大学 一种羰基稠合的硼氮衍生物及其制备方法和应用

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