WO2023151394A1 - Fluorene derivative and use thereof - Google Patents

Fluorene derivative and use thereof Download PDF

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WO2023151394A1
WO2023151394A1 PCT/CN2022/140610 CN2022140610W WO2023151394A1 WO 2023151394 A1 WO2023151394 A1 WO 2023151394A1 CN 2022140610 W CN2022140610 W CN 2022140610W WO 2023151394 A1 WO2023151394 A1 WO 2023151394A1
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French (fr)
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曹建华
朱波
王志杰
唐伟
李程辉
徐先锋
刘赛赛
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上海八亿时空先进材料有限公司
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Definitions

  • the invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and its application.
  • the organic light-emitting phenomenon refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light and heat are emitted.
  • Metal complex phosphorescent materials that utilize triplet state emission have high luminous efficiency, and their green and red light materials have met the requirements for use, but metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels and Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current OLED development.
  • the present invention provides the following technical solutions:
  • the present invention provides a kind of fluorene derivative, its structural formula is as shown in formula (I):
  • Ar 1 is selected from C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C A group consisting of 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 -C 60 arylamino, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl;
  • Each Z is independently selected from CR 10 or N;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 2 -C 60 heterocyclic aryl or a group consisting of formula (II), any adjacent two One or more groups may optionally be joined or fused to form additional one or more substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S;
  • Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted C 6 -C 60 aryl groups, substituted or unsubstituted C 6 -C 60 condensed ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamines group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
  • n is an integer selected from 0 to 5;
  • L is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
  • the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
  • Ar is selected from methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 arylamino, or substituted or A group consisting of unsubstituted C 2 -C 60 heterocyclic aryl groups;
  • Ar 2 and Ar 3 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 arylamino group, or a substituted or unsubstituted C 2 -C 60 heterocycle A group consisting of aryl groups;
  • Z is selected from CR 10 ;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 6 -C 60 aryl , a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group or a group consisting of formula (II);
  • n is selected from 0, 1 or 2.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently hydrogen or a group represented by formula (II).
  • the C 2 -C 60 heterocyclic aryl group is selected from the group consisting of the following groups shown in II-1 to II-17:
  • Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
  • T 1 means O, S, CR'R" or NAr';
  • R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
  • Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
  • the L is selected from a single bond or a group consisting of the following groups shown in III-1 to III-15:
  • Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane group, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 60 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
  • Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 arylsulfide group, or a substituted or unsubstituted One or more of the C 2 -C 60 heterocyclic aryl groups;
  • T 2 represents O, S, CR'R" or NAr';
  • R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
  • Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
  • the C 6 -C 60 aryl group of the present invention especially refers to a group derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, tripolyphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotripolyindene, spirothree polyindene, spiroisotripolyindene, furan, Benzofuran, isobenzofuran, dibenzofuran,
  • substituted or unsubstituted refers to a group selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxyl acid salt, sulfonic acid group or its sulfonate, phosphoric acid group or its phosphate salt, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkyl, C 3 -C 60 cycloalkenyl, C 6 -C 60 aryl, C 6 -C 60 aryloxy, C 6 -C 60
  • the aryl sulfide group and the C 2 -C 60 heterocyclic aryl group are substituted or unsubstituted with one or more substituents, or a substituent formed by
  • the structural formula of the fluorene derivative is selected from the group consisting of the following C473 to C583:
  • *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
  • the present invention also provides an organic electroluminescent material, the raw material of which comprises the above-mentioned fluorene derivative; the organic electroluminescent material comprising the fluorene derivative of the present invention has the capability of carrier transport or light extraction.
  • the organic electroluminescence material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a CPL layer material or an electron blocking layer Material.
  • the present invention also provides the application of the above-mentioned fluorene derivatives in the preparation of organic electroluminescent elements.
  • the present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a CPL layer, and more than one organic layer placed between the first electrode and the second electrode; At least one of the organic layer and the CPL layer includes the above-mentioned fluorene derivative.
  • the organic electroluminescent element comprises a cathode, an anode, a CPL and at least one light emitting layer. Besides these layers it may also contain further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, excitation layers, sub-blocking layer, electron blocking layer and/or charge generating layer. Interlayers having, for example, an exciton-blocking function can likewise be introduced between two emitting layers. It should be noted, however, that not every one of these layers is required to be present.
  • the organic electroluminescence element described here may comprise one light-emitting layer, or it may comprise a plurality of light-emitting layers.
  • various light-emitting compounds capable of emitting light are used in the light-emitting layer.
  • Particular preference is given to systems with three emitting layers, the three layers being able to exhibit blue, green and red emission. If more than one emitting layer is present, according to the invention at least one of these layers comprises a compound according to the invention.
  • the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer and the hole injection layer or The anode is directly adjacent, and/or the emissive layer is directly adjacent to the electron transport or electron injection layer or the cathode.
  • organic electroluminescent components in which one or more layers can be applied by means of a sublimation process by vapor deposition in a vacuum sublimation apparatus at an initial pressure below 10 ⁇ 5 Pa, preferably below 10 ⁇ 6 Pa to apply the material.
  • the initial pressure may also be even lower, for example below 10 ⁇ 7 Pa.
  • a particular example of this method is the organic vapor jet printing method, in which the material is applied directly via a nozzle and is thus structured.
  • organic electroluminescent elements which, from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, spray Ink printing or nozzle printing to produce one or more layers.
  • Soluble compounds are obtained, for example, by appropriately substituting the compound represented by formula (I).
  • These methods are also particularly suitable for oligomers, dendrimers and polymers.
  • hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
  • the invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, comprising applying at least one layer by means of a sublimation method and/or applying at least one layer by means of an organic vapor deposition method or by means of sublimation of a carrier gas , and/or apply at least one layer from solution by spin coating or by means of a printing method.
  • the present invention relates to compounds comprising at least one of the above indicated compounds of the invention.
  • the compounds can preferably also comprise further compounds.
  • Processing of the compounds of the invention from the liquid phase requires processing of formulations of the compounds of the invention which may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenzone, 1,2,3,5-tetramethylbenzene, 1,2, 4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisole, 3,5-Dimethylanisole, Acetophenone, ⁇ -Terpineol, Benzothiazole, Butyl Benzoate, Cumene, Cyclohexanol, Cyclohe
  • the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL layer or an electron blocking layer.
  • the present invention also provides a consumer product, which includes the above-mentioned organic electroluminescent element.
  • the raw materials used in the present invention can be obtained commercially, and any range described in the present invention includes the end value and any value between the end value and the end value or any value between the end value Any subrange formed by .
  • the fluorene derivative shown in the formula (I) provided by the present invention increases the rigidity of triarylamine, has a high triplet energy level, improves the thermal stability of the material and the ability to transport carriers; the fluorene derivative Applied in organic electroluminescent elements, the driving voltage can be significantly reduced, and the luminous efficiency and lifespan can be improved.
  • Fig. 1 is a schematic diagram containing a CPL layer of an organic electroluminescent element of the present invention
  • 100 is an organic electroluminescent element
  • 101 is a substrate
  • 102 is an anode layer
  • 103 is a hole injection layer
  • 104 is a hole transport layer
  • 105 is an electron blocking layer
  • 106 is a light-emitting layer
  • 107 is a hole Blocking layer
  • 108 is an electron transport layer
  • 109 is an electron injection layer
  • 110 is a cathode layer
  • 111 is a CPL layer.
  • Fig. 2 is a schematic diagram of an organic electroluminescent element of the present invention that does not contain a hole blocking layer;
  • 200 is an organic electroluminescent element
  • 101 is a substrate
  • 102 is an anode layer
  • 103 is a hole injection layer
  • 104 is a hole transport layer
  • 105 is an electron blocking layer
  • 106 is a light-emitting layer
  • 107 is an electron transport layer.
  • Layer, 108 is the electron injection layer
  • 109 is the cathode layer
  • 110 is the CPL layer.
  • Luminance and chromaticity coordinates tested using spectral scanner PhotoResearch PR-715;
  • X 1 represents I, Br, Cl or OTf; one of R 1 to R 9 in I-0 to I-4 is halogen or OTf, and other symbols used are as defined above.
  • the preparation method of compound C-1 comprises the steps:
  • the first step preparation of intermediate Int-1
  • the preparation method of compound C500 comprises the steps:
  • the first step the preparation of intermediate Int-5
  • the preparation method of compound C580 comprises the following steps:
  • the preparation method of compound C540 comprises the steps:
  • the first step preparation of compound Int-20
  • a kind of organic electroluminescent element 200 comprises substrate 101, is arranged on the anode layer 102 on the substrate 101, is arranged on the hole injection layer 103 on the anode layer 102, is arranged on the hole injection layer
  • the electron injection layer 108 on the transport layer 107, the cathode layer 109 arranged on the electron injection layer 108, and the CPL layer 110 arranged on the cathode layer, its preparation method comprises the following steps:
  • the glass substrate coated with the ITO conductive layer is ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in acetone/ethanol mixed solvent for 30 minutes, and baked in a clean environment until completely dry, Irradiate with a UV light cleaner for 10 minutes and bombard the surface with a low-energy positive ion beam.
  • Metal magnesium and silver are vapor-deposited on the electron injection layer as a transparent cathode layer, the mass ratio of magnesium and silver is 1:2, and the thickness of the vapor-deposited film is
  • a kind of organic electroluminescent element 100 comprises substrate 101, is arranged on the anode layer 102 on the substrate 101, is arranged on the hole injection layer 103 on the anode layer 102, is arranged on the hole injection layer
  • the performance detection data of the obtained element is normalized with reference to the comparative element 1, and the results are listed in Table 9, wherein the driving voltage, luminous efficiency and half-maximum width (FWHM) are obtained when the current density of the element is 10mA/cm 2
  • FWHM half-maximum width
  • the light-emitting element prepared by using the fluorene derivative of the present invention as an electron-blocking material also has a lower driving voltage than B-1, B-2, and B-3 under the condition of 10mA/cm 2 , especially compound C555 (T 3 is CMe 2 )
  • the luminous efficiency is significantly improved, and the LT95% lifetime under the initial condition of the current density of 50mA/cm 2 has obvious advantages.

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Abstract

The present invention relates to the technical field of organic electroluminescent materials, and in particular, to a fluorene derivative and a use thereof. The structural formula of the fluorene derivative is shown in formula (I). The fluorene derivative shown in formula (I) provided by the present invention increases the rigidity of triarylamine, has a high triplet energy level, and improves the thermal stability and carrier transport capability of materials. When the fluorene derivative is applied to an organic electroluminescent element, the driving voltage can be remarkably reduced, the light-emitting efficiency can be improved, and the service life can be prolonged.

Description

一种芴衍生物及其应用A kind of fluorene derivative and its application
交叉引用cross reference
本申请要求2022年2月14日提交的专利名称为“一种芴衍生物及其应用”的第202210135591.8号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。This application claims the priority of the Chinese patent application No. 202210135591.8 filed on February 14, 2022 with the patent title “A Fluorene Derivative and Its Application”, the entire disclosure content of which is incorporated herein by reference in its entirety.
技术领域technical field
本发明涉及有机电致发光材料技术领域，尤其涉及一种芴衍生物及其应用。The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and its application.
背景技术Background technique
一般而言，有机发光现象是指在对有机物质施加电能时发出光的现象；即在阳极与阴极之间配置有机层时，如果在两个电极之间施加电压，则空穴会从阳极注入至有机层，电子会从阴极注入至有机层；当所注入的空穴和电子相遇时，会形成激子，当该激子跃迁至基态时，会发出光和热。Generally speaking, the organic light-emitting phenomenon refers to the phenomenon of emitting light when electric energy is applied to an organic substance; that is, when an organic layer is arranged between an anode and a cathode, if a voltage is applied between the two electrodes, holes will be injected from the anode To the organic layer, electrons are injected from the cathode to the organic layer; when the injected holes and electrons meet, excitons are formed, and when the excitons transition to the ground state, light and heat are emitted.
最近几年有机电致发光显示技术己趋于成熟，一些产品已进入市场，但在产业化过程中，仍有许多问题亟待解决。特别是用于制作元件的各种有机材料，其载流子注入和传输性能、材料电发光性能、使用寿命、色纯度、各种材料之间及与各电极之间的匹配等，尚有许多问题还未解决；尤其是发光元件的发光效率和使用寿命还达不到实用化要求，这大大限制了OLED技术的发展。而利用三线态发光的金属配合物磷光材料具有高的发光效率，其绿光和红光材料已经达到使用要求，但是金属配合物磷光材料要求具有高三线态能级的磷光材料或空穴材料与之匹配，因此，开发具有高三线态能级的磷光材料或空穴材料是当前OLED发展的迫切需求。In recent years, organic electroluminescent display technology has become mature, and some products have entered the market, but there are still many problems to be solved in the process of industrialization. Especially for various organic materials used to make components, there are still many problems in their carrier injection and transport performance, material electroluminescence performance, service life, color purity, matching between various materials and between electrodes, etc. The problem has not been solved; especially the luminous efficiency and service life of the light-emitting element have not yet met the practical requirements, which greatly limits the development of OLED technology. Metal complex phosphorescent materials that utilize triplet state emission have high luminous efficiency, and their green and red light materials have met the requirements for use, but metal complex phosphorescent materials require phosphorescent materials or hole materials with high triplet energy levels and Therefore, the development of phosphorescent materials or hole materials with high triplet energy levels is an urgent need for the current OLED development.
在目前的技术发展下，无论是对于荧光材料还是对于磷光材料，特别是在用于有机电致发光元件中的工作电压、效率和寿命方面和在升华期间的热稳定性方面，都还需要改进。Under the current technological development, whether it is for fluorescent materials or phosphorescent materials, especially in terms of operating voltage, efficiency and lifetime used in organic electroluminescent elements and thermal stability during sublimation, there is still a need for improvement .
由此，为了克服如上所述的以往技术问题而进一步提高有机电致发光元件的特性，继续要求对于在有机电致发光元件中可用作磷光材料或空穴材料的更加稳定且有效的物质的开发。Therefore, in order to further improve the characteristics of organic electroluminescent elements by overcoming the above-mentioned conventional technical problems, there is a continuous demand for more stable and effective substances that can be used as phosphorescent materials or hole materials in organic electroluminescent elements. develop.
鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
本发明的目的在于提供一种芴衍生物，该芴衍生物有效提高了材料热稳定性和输送载流子的能力，利用该芴衍生物制备的有机电致发光元件可显著降低驱动电压、提高发光效率和寿命；本发明的另一目的在于提供该芴衍生物的应用。The object of the present invention is to provide a fluorene derivative, which effectively improves the thermal stability of the material and the ability to transport carriers, and the organic electroluminescent element prepared by using the fluorene derivative can significantly reduce the driving voltage, increase the Luminous efficiency and lifetime; Another object of the present invention is to provide the application of the fluorene derivative.
具体地，本发明提供以下技术方案：Specifically, the present invention provides the following technical solutions:
本发明提供一种芴衍生物，其结构式如式(I)所示：The present invention provides a kind of fluorene derivative, its structural formula is as shown in formula (I):
Figure PCTCN2022140610-appb-000001
Figure PCTCN2022140610-appb-000001
其中，in,
Ar 1选自由C 1-C 40的烷基、C 3-C 40的环烷基或带有支链的烷基、取代或未取代的C 6-C 60 芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 1 is selected from C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C A group consisting of 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 -C 60 arylamino, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl;
Z各自独立地选自CR 10或N； Each Z is independently selected from CR 10 or N;
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自由氢、氘、卤素、腈基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 2-C 60杂环芳基或式(II)组成的群组，任意相邻的两个或多个基团可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 2 -C 60 heterocyclic aryl or a group consisting of formula (II), any adjacent two One or more groups may optionally be joined or fused to form additional one or more substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S;
式(II)的结构式如下：The structural formula of formula (II) is as follows:
Figure PCTCN2022140610-appb-000002
Figure PCTCN2022140610-appb-000002
Ar 2、Ar 3各自独立地选自由取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted C 6 -C 60 aryl groups, substituted or unsubstituted C 6 -C 60 condensed ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamines group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
m选自0～5的整数；m is an integer selected from 0 to 5;
L选自单键、取代或未取代的C 6-C 60的亚芳基、或者取代或未取代的C 2-C 60亚杂芳基； L is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
*—表示式(II)与式(I)的连接键。*—represents the link between formula (II) and formula (I).
本发明中，相邻基团彼此结合而形成的取代或未取代的环中，“环”是指取代或未取代的烃环、或者取代或未取代的杂环。In the present invention, in a substituted or unsubstituted ring formed by bonding adjacent groups, the "ring" refers to a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.
作为优选，Ar 1选自由甲基、乙基、环戊基、环己基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Preferably, Ar is selected from methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 arylamino, or substituted or A group consisting of unsubstituted C 2 -C 60 heterocyclic aryl groups;
Ar 2、Ar 3各自独立地选自由取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 2 and Ar 3 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 arylamino group, or a substituted or unsubstituted C 2 -C 60 heterocycle A group consisting of aryl groups;
Z选自CR 10； Z is selected from CR 10 ;
R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自由氢、氘、取代或未取代的C 6-C 60芳基、取代或未取代的C 2-C 60杂环芳基或式(II)组成的群组； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 6 -C 60 aryl , a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group or a group consisting of formula (II);
m选自0、1或2。m is selected from 0, 1 or 2.
进一步地，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地为氢或式(II)所示基团。 Further, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently hydrogen or a group represented by formula (II).
作为优选，所述C 2-C 60杂环芳基选自由以下II-1～II-17所示基团组成的群组： Preferably, the C 2 -C 60 heterocyclic aryl group is selected from the group consisting of the following groups shown in II-1 to II-17:
Figure PCTCN2022140610-appb-000003
Figure PCTCN2022140610-appb-000003
其中，in,
Z 1、Z 2各自独立地选自由氢、氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1-C 60烷基、C 2-C 60烯基、C 2-C 60炔基、C 1-C 60烷氧基、C 3-C 60环烷烃基、C 3-C 60环烯烃基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
x1表示1-4的整数；x2表示1-3的整数；x3表示1或2；x4表示1-6的整数；x5表示1-5的整数；x1 represents an integer of 1-4; x2 represents an integer of 1-3; x3 represents an integer of 1 or 2; x4 represents an integer of 1-6; x5 represents an integer of 1-5;
T 1表示O、S、CR’R”或NAr’； T 1 means O, S, CR'R" or NAr';
R’、R”各自独立地选自由氢、氘、C 1-C 60的烷基、C 1-C 60的杂烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
Ar’选自由C 1-C 60的烷基、C 1-C 60的杂烷基、C 3-C 60的环烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
Figure PCTCN2022140610-appb-000004
表示取代基与主体结构的连接键。
Figure PCTCN2022140610-appb-000004
Indicates the link between the substituent and the main structure.
作为优选，所述L选自单键或由以下III-1～III-15所示基团组成的群组：Preferably, the L is selected from a single bond or a group consisting of the following groups shown in III-1 to III-15:
Figure PCTCN2022140610-appb-000005
Figure PCTCN2022140610-appb-000005
其中，in,
Z 11、Z 12各自独立地选自由氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1-C 60的烷基、C 2-C 60的烯基、C 2-C 60的炔基、C 1-C 60的烷氧基、C 3-C 60的环烷烃基、C 3-C 60的环烯烃基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane group, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 60 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
Z 13表示取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基中的一种或多种； Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 arylsulfide group, or a substituted or unsubstituted One or more of the C 2 -C 60 heterocyclic aryl groups;
y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer of 1-4; y2 represents an integer of 1-6; y3 represents an integer of 1-3; y4 represents an integer of 1-5;
T 2表示O、S、CR’R”或NAr’； T 2 represents O, S, CR'R" or NAr';
R’、R”各自独立地选自由氢、氘、C 1-C 60的烷基、C 1-C 60的杂烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
Ar’选自由C 1-C 60的烷基、C 1-C 60的杂烷基、C 3-C 60的环烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
Figure PCTCN2022140610-appb-000006
表示取代基与主体结构的连接键。
Figure PCTCN2022140610-appb-000006
Indicates the link between the substituent and the main structure.
本发明的C 6-C 60芳基，特别是指衍生自如下物质的基团：苯、萘、蒽、苯并蒽、菲、芘、
Figure PCTCN2022140610-appb-000007
苝、荧蒽、并四苯、并五苯、苯并芘、联苯、偶苯、三联苯、三聚苯、芴、螺二芴、二氢菲、二氢芘、四氢芘、顺式或反式茚并芴、顺式或反式茚并咔唑、顺式或反式吲哚并咔唑、三聚茚、异三聚茚、螺三聚茚、螺异三聚茚、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、二苯并噻吩、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并[5,6]喹啉、苯并[6,7]喹啉、苯并[7,8]喹啉、吩噻嗪、吩噁嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、噁唑、苯并噁唑、萘并噁唑、蒽并噁唑、菲并噁唑、异噁唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、六氮杂苯并菲、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、1,5-二氮杂蒽、2,7-二氮杂芘、2,3-二氮杂芘、1,6-二氮杂芘、1,8-二氮杂芘、4,5-二氮杂芘，4,5,9,10-四氮杂苝、吡嗪、吩嗪、吩噁嗪、吩噻嗪、荧红环、萘啶、氮杂咔唑、苯并咔啉、咔啉、菲咯啉、1,2,3-***、1,2,4-***、苯并***、1,2,3-噁二唑、1,2,4-噁二唑、1,2,5-噁二唑、1,3,4-噁二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑、1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、吲嗪、喹唑啉和苯并噻二唑或者衍生自这些体系的组合的基团。 The C 6 -C 60 aryl group of the present invention especially refers to a group derived from the following substances: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,
Figure PCTCN2022140610-appb-000007
Perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, tripolyphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis Or trans indenofluorene, cis or trans indenocarbazole, cis or trans indolocarbazole, tripolyindene, isotripolyindene, spirothree polyindene, spiroisotripolyindene, furan, Benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline , acridine, phenanthridine, benzo[5,6]quinoline, benzo[6,7]quinoline, benzo[7,8]quinoline, phenothiazine, phenoxazine, pyrazole, indazole , imidazole, benzimidazole, naphthimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthoxazole, anthraxazole, phenanthrene Oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazatriphenylene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1, 5-diazapyrene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene Pyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorochrome, naphthyridine, azacarbazole, benzocarboline, carboline, phenanthrene oxadiazole, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2, 5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3, 4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2 , 3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine, quinazoline and benzothiadiazole or groups derived from combinations of these systems.
本发明中，“取代或未取代的”这一用语是指，被选自氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1-C 60的烷基、C 2-C 60的烯基、C 2-C 60的炔基、C 1-C 60的烷氧基、C 3-C 60的环烷基、C 3-C 60的环烯基、C 6-C 60的芳基、C 6-C 60的芳氧基、C 6-C 60的芳硫醚基和C 2-C 60的杂环芳基中的1个以上的取代基取代或未取代，或者被上述例示的取代基中的2个以上的取代基连接而成的取代基取代或未取代。 In the present invention, the term "substituted or unsubstituted" refers to a group selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxyl acid salt, sulfonic acid group or its sulfonate, phosphoric acid group or its phosphate salt, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkyl, C 3 -C 60 cycloalkenyl, C 6 -C 60 aryl, C 6 -C 60 aryloxy, C 6 -C 60 The aryl sulfide group and the C 2 -C 60 heterocyclic aryl group are substituted or unsubstituted with one or more substituents, or a substituent formed by connecting two or more substituents among the substituents exemplified above Substituted or not.
作为优选，所述芴衍生物的结构式选自由以下C473至C583组成的群组：Preferably, the structural formula of the fluorene derivative is selected from the group consisting of the following C473 to C583:
Figure PCTCN2022140610-appb-000008
Figure PCTCN2022140610-appb-000008
Figure PCTCN2022140610-appb-000009
Figure PCTCN2022140610-appb-000009
Figure PCTCN2022140610-appb-000010
Figure PCTCN2022140610-appb-000010
Figure PCTCN2022140610-appb-000011
Figure PCTCN2022140610-appb-000011
Figure PCTCN2022140610-appb-000012
Figure PCTCN2022140610-appb-000012
Figure PCTCN2022140610-appb-000013
Figure PCTCN2022140610-appb-000013
其中，*—T 3—*选自*—O—*、*—S—*或下述结构中的一种： Wherein, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
Figure PCTCN2022140610-appb-000014
Figure PCTCN2022140610-appb-000014
*—和—*表示连接键。*— and —* indicate connecting keys.
本发明还提供一种有机电致发光材料，其原料包括以上所述的芴衍生物；包括本发明的芴衍生物的有机电致发光材料具有载流子传输的能力或光取出能力。The present invention also provides an organic electroluminescent material, the raw material of which comprises the above-mentioned fluorene derivative; the organic electroluminescent material comprising the fluorene derivative of the present invention has the capability of carrier transport or light extraction.
作为优选，所述有机电致发光材料为空穴注入层材料、空穴传输层材料、空穴阻挡层材 料、发光层材料、电子传输层材料、电子注入层材料、CPL层材料或电子阻挡层材料。Preferably, the organic electroluminescence material is a hole injection layer material, a hole transport layer material, a hole blocking layer material, a light emitting layer material, an electron transport layer material, an electron injection layer material, a CPL layer material or an electron blocking layer Material.
本发明同时提供以上所述的芴衍生物在制备有机电致发光元件中的应用。The present invention also provides the application of the above-mentioned fluorene derivatives in the preparation of organic electroluminescent elements.
本发明还提供一种有机电致发光元件，其包括：第一电极、第二电极、CPL层和置于所述第一电极、所述第二电极之间的一层以上的有机层；所述有机层、CPL层中的至少一层包括以上所述的芴衍生物。The present invention also provides an organic electroluminescent element, which includes: a first electrode, a second electrode, a CPL layer, and more than one organic layer placed between the first electrode and the second electrode; At least one of the organic layer and the CPL layer includes the above-mentioned fluorene derivative.
所述有机电致发光元件包含阴极、阳极、CPL和至少一个发光层。除了这些层之外，它还可以包含其它的层，例如在每种情况下，包含一个或多个空穴注入层、空穴传输层、空穴阻挡层、电子传输层、电子注入层、激子阻挡层、电子阻挡层和/或电荷产生层。具有例如激子阻挡功能的中间层同样可引入两个发光层之间。然而，应当指出，这些层中的每个并非必须都存在。此处所述有机电致发光元件可包含一个发光层，或者它可包含多个发光层。即，将能够发光的多种发光化合物用于所述发光层中。特别优选具有三个发光层的体系，其中所述三个层可显示蓝色、绿色和红色发光。如果存在多于一个的发光层，则根据本发明，这些层中的至少一个层包含本发明的化合物。The organic electroluminescent element comprises a cathode, an anode, a CPL and at least one light emitting layer. Besides these layers it may also contain further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, excitation layers, sub-blocking layer, electron blocking layer and/or charge generating layer. Interlayers having, for example, an exciton-blocking function can likewise be introduced between two emitting layers. It should be noted, however, that not every one of these layers is required to be present. The organic electroluminescence element described here may comprise one light-emitting layer, or it may comprise a plurality of light-emitting layers. That is, various light-emitting compounds capable of emitting light are used in the light-emitting layer. Particular preference is given to systems with three emitting layers, the three layers being able to exhibit blue, green and red emission. If more than one emitting layer is present, according to the invention at least one of these layers comprises a compound according to the invention.
进一步地，根据本发明的有机电致发光元件不包含单独的空穴注入层和/或空穴传输层和/或空穴阻挡层和/或电子传输层，即发光层与空穴注入层或阳极直接相邻，和/或发光层与电子传输层或电子注入层或阴极直接相邻。Further, the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light-emitting layer and the hole injection layer or The anode is directly adjacent, and/or the emissive layer is directly adjacent to the electron transport or electron injection layer or the cathode.
在根据本发明的有机电致发光元件的其它层中，特别是在空穴传输层中和发光层中以及在CPL中，所有材料可以按照根据现有技术通常所使用的方式来使用。本领域普通技术人员因此将能够在不付出创造性劳动的情况下与根据本发明的发光层组合使用关于有机电致发光元件所知的所有材料。In the other layers of the organic electroluminescent component according to the invention, in particular in the hole-transport layer and in the emitting layer and in the CPL, all materials can be used in the manner customarily used according to the prior art. A person skilled in the art will therefore be able to use all materials known for organic electroluminescent elements in combination with the emitting layer according to the invention without inventive step.
此外优选如下的有机电致发光元件，可以借助于升华方法施加一个或多个层，其中在真空升华装置中在低于10 -5Pa、优选低于10 -6Pa的初压下通过气相沉积来施加所述材料。然而，所述初压还可能甚至更低，例如低于10 -7Pa。 Furthermore, preference is given to organic electroluminescent components in which one or more layers can be applied by means of a sublimation process by vapor deposition in a vacuum sublimation apparatus at an initial pressure below 10 −5 Pa, preferably below 10 −6 Pa to apply the material. However, the initial pressure may also be even lower, for example below 10 −7 Pa.
同样优选如下的有机电致发光元件，也可以借助于有机气相沉积方法或借助于载气升华来施加一个或多个层，其中，在10 -5Pa至1Pa之间的压力下施加所述材料。该方法的特别的例子是有机蒸气喷印方法，其中所述材料通过喷嘴直接施加，并且因此是结构化的。 Preference is likewise given to organic electroluminescent elements in which one or more layers can also be applied by means of organic vapor deposition methods or by means of sublimation of a carrier gas, wherein the material is applied at a pressure between 10 −5 Pa and 1 Pa . A particular example of this method is the organic vapor jet printing method, in which the material is applied directly via a nozzle and is thus structured.
此外优选如下的有机电致发光元件，从溶液中，例如通过旋涂，或借助于任何所希望的印刷方法例如丝网印刷、柔性版印刷、平版印刷、光引发热成像、热转印、喷墨印刷或喷嘴印刷，来产生一个或多个层。可溶性化合物，例如通过适当的取代式(I)所示的化合物获得可溶性化合物。这些方法也特别适于低聚物、树枝状大分子和聚合物。此外可行的是混合方法，其中例如从溶液中施加一个或多个层并且通过气相沉积施加一个或多个另外的层。Furthermore, preference is given to organic electroluminescent elements which, from solution, for example by spin coating, or by means of any desired printing method, such as screen printing, flexographic printing, lithography, photoinduced thermography, thermal transfer, spray Ink printing or nozzle printing to produce one or more layers. Soluble compounds are obtained, for example, by appropriately substituting the compound represented by formula (I). These methods are also particularly suitable for oligomers, dendrimers and polymers. Also possible are hybrid methods in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
这些方法是本领域普通技术人员通常已知的，并且他们可以在不付出创造性劳动的情况下将其应用于包含根据本发明的化合物的有机电致发光元件。These methods are generally known to those skilled in the art and they can apply them without inventive effort to organic electroluminescent components comprising the compounds according to the invention.
因此，本发明还涉及制造根据本发明的有机电致发光元件的方法，包括借助于升华方法来施加至少一个层，和/或借助于有机气相沉积方法或借助于载气升华来施加至少一个层，和/或从溶液中通过旋涂或借助于印刷方法来施加至少一个层。The invention therefore also relates to a method for producing an organic electroluminescent element according to the invention, comprising applying at least one layer by means of a sublimation method and/or applying at least one layer by means of an organic vapor deposition method or by means of sublimation of a carrier gas , and/or apply at least one layer from solution by spin coating or by means of a printing method.
此外，本发明涉及包含至少一种上文指出的本发明的化合物。如上文关于有机电致发光元件指出的相同优选情况适用于所述本发明的化合物。特别是，所述化合物此外还可优选包含其它化合物。从液相处理本发明的化合物，例如通过旋涂或通过印刷方法进行处理，需要处理本发明的化合物的制剂，这些制剂可以例如是溶液、分散体或乳液。出于这个目的、可优选使用两种或更多种溶剂的混合物。合适并且优选的溶剂例如是甲苯、苯甲醚、邻二甲苯、间二甲苯或对二甲苯、苯甲酸甲酯、均三甲苯、萘满、邻二甲氧基苯、四氢呋喃、甲基四氢呋喃、四氢吡喃、氯苯、二噁烷、苯氧基甲苯，特别是3-苯氧基甲苯、(-)-葑酮、1,2,3,5-四甲基苯、1,2,4,5-四甲基苯、1-甲基萘、2-甲基苯并噻唑、2-苯氧基乙醇、2-吡咯烷酮、3-甲 基苯甲醚、4-甲基苯甲醚、3,4-二甲基苯甲醚、3,5-二甲基苯甲醚、苯乙酮、α-萜品醇、苯并噻唑、苯甲酸丁酯、异丙苯、环己醇、环己酮、环己基苯、十氢化萘、十二烷基苯、苯甲酸乙酯、茚满、苯甲酸甲酯、1-甲基吡咯烷酮、对甲基异丙基苯、苯***、1,4-二异丙基苯、二苄醚、二乙二醇丁基甲基醚、三乙二醇丁基甲基醚、二乙二醇二丁基醚、三乙二醇二甲基醚、二乙二醇单丁基醚、三丙二醇二甲基醚、四乙二醇二甲基醚、2-异丙基萘、戊苯、己苯、庚苯、辛苯、1,1-双(3,4-二甲基苯基)乙烷，或这些溶剂的混合物。Furthermore, the present invention relates to compounds comprising at least one of the above indicated compounds of the invention. The same preferences as indicated above for organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds can preferably also comprise further compounds. Processing of the compounds of the invention from the liquid phase, for example by spin coating or by printing methods, requires processing of formulations of the compounds of the invention which may be, for example, solutions, dispersions or emulsions. For this purpose, mixtures of two or more solvents may preferably be used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, Tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenzone, 1,2,3,5-tetramethylbenzene, 1,2, 4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-Dimethylanisole, 3,5-Dimethylanisole, Acetophenone, α-Terpineol, Benzothiazole, Butyl Benzoate, Cumene, Cyclohexanol, Cyclohexanol Hexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1,4 -Diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol mono Butyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-di methylphenyl)ethane, or a mixture of these solvents.
作为优选，所述有机层包括空穴注入层、空穴传输层、空穴阻挡层、发光层、电子传输层、电子注入层、CPL层或电子阻挡层。Preferably, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL layer or an electron blocking layer.
本发明还提供一种消费型产品，其包括以上所述的有机电致发光元件。The present invention also provides a consumer product, which includes the above-mentioned organic electroluminescent element.
另外，如无特殊说明，本发明中所用原料均可通过市售商购获得，本发明所记载的任何范围包括端值以及端值之间的任何数值以及端值或者端值之间的任意数值所构成的任意子范围。In addition, unless otherwise specified, the raw materials used in the present invention can be obtained commercially, and any range described in the present invention includes the end value and any value between the end value and the end value or any value between the end value Any subrange formed by .
本发明所取得的有益效果：The beneficial effect that the present invention obtains:
本发明提供的式(I)所示的芴衍生物，增大了三芳胺的刚性，具有高的三线态能级，提高了材料热稳定性和输送载流子的能力；将该芴衍生物应用在有机电致发光元件中，可显著降低驱动电压、提高发光效率和寿命。The fluorene derivative shown in the formula (I) provided by the present invention increases the rigidity of triarylamine, has a high triplet energy level, improves the thermal stability of the material and the ability to transport carriers; the fluorene derivative Applied in organic electroluminescent elements, the driving voltage can be significantly reduced, and the luminous efficiency and lifespan can be improved.
附图说明Description of drawings
图1是本发明的有机电致发光元件的一个含有CPL层的示意图；Fig. 1 is a schematic diagram containing a CPL layer of an organic electroluminescent element of the present invention;
图1中，100是有机电致发光元件，101是基板，102是阳极层，103是空穴注入层，104是空穴传输层，105是电子阻挡层，106是发光层，107是空穴阻挡层，108是电子传输层，109是电子注入层，110是阴极层，111是CPL层。In Fig. 1, 100 is an organic electroluminescent element, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light-emitting layer, and 107 is a hole Blocking layer, 108 is an electron transport layer, 109 is an electron injection layer, 110 is a cathode layer, 111 is a CPL layer.
图2是本发明的有机电致发光元件的一个不含空穴阻挡层的示意图；Fig. 2 is a schematic diagram of an organic electroluminescent element of the present invention that does not contain a hole blocking layer;
图2中，200是有机电致发光元件，101是基板，102是阳极层，103是空穴注入层，104是空穴传输层，105是电子阻挡层，106是发光层，107是电子传输层，108是电子注入层，109是阴极层，110是CPL层。In Fig. 2, 200 is an organic electroluminescent element, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light-emitting layer, and 107 is an electron transport layer. Layer, 108 is the electron injection layer, 109 is the cathode layer, 110 is the CPL layer.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
在本发明的描述中，除非另有说明，“多个”的含义是两个或两个以上；术语“上”、“下”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, unless otherwise specified, the meaning of "plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower" and so on is based on the orientation or position shown in the drawings. The positional relationship is only for the convenience of describing the present invention and simplifying the description, but does not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention.
以下实施例中所使用的实验方法如无特殊说明，均为常规方法。以下实施例中所用的实验原料和相关设备等，如无特殊说明，均可从商业途径得到，所述百分比如无特殊说明，均为质量百分比。The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental raw materials and related equipment used in the following examples can be obtained from commercial sources unless otherwise specified, and the stated percentages are all mass percentages unless otherwise specified.
下述实施例对OLED材料及元件进行性能测试的测试仪器及方法如下：The testing apparatus and method that following embodiment carries out performance test to OLED material and element are as follows:
OLED元件性能检测条件：OLED component performance testing conditions:
亮度和色度坐标：使用光谱扫描仪PhotoResearch PR-715测试；Luminance and chromaticity coordinates: tested using spectral scanner PhotoResearch PR-715;
电流密度和起亮电压：使用数字源表Keithley 2420测试；Current density and lighting voltage: Tested with Keithley 2420 digital source meter;
功率效率：使用NEWPORT 1931-C测试。Power Efficiency: Tested using NEWPORT 1931-C.
实施例Example
式(I)所示化合物的合成路线如下：The synthetic route of compound shown in formula (I) is as follows:
Figure PCTCN2022140610-appb-000015
Figure PCTCN2022140610-appb-000015
其中，X 1表示I、Br、Cl或OTf；在I-0至I-4中的R 1～R 9中其中之一为卤素或OTf，其它所用符号如上文中所定义。 Wherein, X 1 represents I, Br, Cl or OTf; one of R 1 to R 9 in I-0 to I-4 is halogen or OTf, and other symbols used are as defined above.
实施例1Example 1
化合物C-1的制备方法，包括如下步骤：The preparation method of compound C-1, comprises the steps:
第一步：中间体Int-1的制备The first step: preparation of intermediate Int-1
Figure PCTCN2022140610-appb-000016
Figure PCTCN2022140610-appb-000016
20.0mmol的1-溴-8-萘甲酸、50.0mmol的双(4-氯苯基)碘三氟甲磺酸盐、2.0mmol的醋酸钯和20.0mmol的叔丁醇钠以及100mL的二甲苯，通入氮气保护，升温至110℃搅拌反应24小时，降到室温，加入100mL的水，分出有机相，水相用乙酸乙酯萃取，收集有机相，干燥，减压浓缩干，过硅胶柱分离纯化，得化合物Int-1，黄色固体，收率：64％。20.0 mmol of 1-bromo-8-naphthoic acid, 50.0 mmol of bis(4-chlorophenyl) iodo triflate, 2.0 mmol of palladium acetate and 20.0 mmol of sodium tert-butoxide and 100 mL of xylene, Pass through nitrogen protection, heat up to 110°C and stir to react for 24 hours, cool down to room temperature, add 100mL of water, separate the organic phase, extract the water phase with ethyl acetate, collect the organic phase, dry, concentrate under reduced pressure, pass through a silica gel column Separation and purification yielded compound Int-1 as a yellow solid, yield: 64%.
第二步：中间体Int-2的制备The second step: the preparation of intermediate Int-2
Figure PCTCN2022140610-appb-000017
Figure PCTCN2022140610-appb-000017
在氮气保护下，22.0mmol的苯硼酸、20.0mmol的Int-1、44.0mmol的无水碳酸钠和60mL的甲苯混合，再加入0.1mmol的Pd(PPh 3) 4催化剂和20mL乙醇以及20mL的水，升温至回流搅拌反应12小时，降至室温，加入100mL饱和盐水溶液，用乙酸乙酯萃取，有机相干燥，过滤，减压浓缩干，用硅胶柱分离纯化，得到黄色固体Int-2，收率：87％。 Under nitrogen protection, mix 22.0mmol of phenylboronic acid, 20.0mmol of Int-1, 44.0mmol of anhydrous sodium carbonate and 60mL of toluene, then add 0.1mmol of Pd(PPh 3 ) 4 catalyst, 20mL of ethanol and 20mL of water , heated to reflux and stirred for 12 hours, cooled to room temperature, added 100mL saturated saline solution, extracted with ethyl acetate, dried the organic phase, filtered, concentrated under reduced pressure to dryness, separated and purified with a silica gel column to obtain a yellow solid Int-2, collected Rate: 87%.
参照上述类似的合成方法，制备以下表1所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 1 were prepared:
表1Table 1
Figure PCTCN2022140610-appb-000018
Figure PCTCN2022140610-appb-000018
Figure PCTCN2022140610-appb-000019
Figure PCTCN2022140610-appb-000019
第三步：化合物Int-3的制备The third step: preparation of compound Int-3
Figure PCTCN2022140610-appb-000020
Figure PCTCN2022140610-appb-000020
在氮气保护下，20.0mmol的中间体Int-2溶于80mL干燥的THF，降温至0℃，滴加入24.0mmol的苯基溴化镁THF溶液，升到室温搅拌反应2小时，滴加入20mL的1M稀盐酸，分出有机相，水相用乙酸乙酯萃取，有机相干燥，减压浓缩干，用硅胶柱分离纯化，得化合物Int-3，白色固体，收率：90％。Under the protection of nitrogen, 20.0 mmol of intermediate Int-2 was dissolved in 80 mL of dry THF, cooled to 0°C, 24.0 mmol of phenylmagnesium bromide THF solution was added dropwise, raised to room temperature and stirred for 2 hours, and 20 mL of 1M dilute hydrochloric acid, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, the organic phase was dried, concentrated under reduced pressure to dryness, separated and purified by silica gel column to obtain compound Int-3 as a white solid, yield: 90%.
第四步：化合物C-1的制备Step 4: Preparation of Compound C-1
Figure PCTCN2022140610-appb-000021
Figure PCTCN2022140610-appb-000021
在氮气保护下，20.0mmol的中间体Int-3溶于50mL干燥的二氯甲烷，降温至0℃，滴加入30.0mmol的三氟化硼***，升到室温搅拌反应1小时，升温回流反应2小时，降到室温，滴加入50mL的10％氢氧化钠水溶液，分出有机相，水相用二氯甲烷萃取，有机相干燥，减压浓缩干，用硅胶柱分离纯化，得化合物C-1，白色固体，收率：92％。Under the protection of nitrogen, 20.0 mmol of intermediate Int-3 was dissolved in 50 mL of dry dichloromethane, cooled to 0°C, and 30.0 mmol of boron trifluoride diethyl ether was added dropwise, raised to room temperature and stirred for 1 hour, then heated to reflux for reaction 2 hour, lowered to room temperature, added dropwise 50mL of 10% sodium hydroxide aqueous solution, separated the organic phase, extracted the aqueous phase with dichloromethane, dried the organic phase, concentrated under reduced pressure to dryness, and separated and purified with a silica gel column to obtain compound C-1 , white solid, yield: 92%.
参照上述类似的合成方法，制备以下表2所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 2 were prepared:
表2Table 2
Figure PCTCN2022140610-appb-000022
Figure PCTCN2022140610-appb-000022
Figure PCTCN2022140610-appb-000023
Figure PCTCN2022140610-appb-000023
参照上述类似的合成方法，仅将苯基溴化镁替换为甲基碘化镁，制备以下表3所示化合物：With reference to the above-mentioned similar synthetic method, only phenylmagnesium bromide is replaced by methylmagnesium iodide, and the compounds shown in the following table 3 are prepared:
表3table 3
Figure PCTCN2022140610-appb-000024
Figure PCTCN2022140610-appb-000024
实施例2Example 2
化合物C500的制备方法，包括如下步骤：The preparation method of compound C500 comprises the steps:
第一步：中间体Int-5的制备The first step: the preparation of intermediate Int-5
Figure PCTCN2022140610-appb-000025
Figure PCTCN2022140610-appb-000025
在氮气保护下，12.0mmol的9-([1,1'-联苯]-3-基)-3-溴-9H-咔唑溶于50mL干燥的THF，降温至-78℃，滴加入14.4mmol的2.5M正丁基锂正己烷溶液，搅拌反应1小时，再滴加入10.0mmol的Int-4溶于THF的溶液，升到室温搅拌反应1小时，滴加入20mL的1M稀盐酸，分出有机相，水相用乙酸乙酯萃取，有机相干燥，减压浓缩干，用硅胶柱分离纯化，得 化合物Int-5，黄色固体，收率：93％。Under nitrogen protection, 12.0 mmol of 9-([1,1'-biphenyl]-3-yl)-3-bromo-9H-carbazole was dissolved in 50 mL of dry THF, cooled to -78°C, and added dropwise to 14.4 2.5M n-butyllithium n-hexane solution of 1 mmol, stirred and reacted for 1 hour, then dropwise added 10.0 mmol of Int-4 solution dissolved in THF, raised to room temperature and stirred for 1 hour, added dropwise 20 mL of 1M dilute hydrochloric acid, separated The organic phase and the aqueous phase were extracted with ethyl acetate, the organic phase was dried, concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain compound Int-5 as a yellow solid, yield: 93%.
第二步：化合物C500的制备The second step: the preparation of compound C500
Figure PCTCN2022140610-appb-000026
Figure PCTCN2022140610-appb-000026
参照实施例1第四步的合成方法，仅将实施例1第四步中的Int-3替换为Int-5，制备化合物C500，白色固体，收率：88％，真空升华后，HPLC：99.96％，MS(MALDI-TOF)：m/z＝608.2308[M+H] +； 1HNMR(δ、CDCl 3)：8.81(1H,s)；8.50(1H,s)；8.25～8.18(4H,m)；8.16～8.13(1H,m)；7.92～7.90(1H,d)；7.75～7.64(8H,m)；7.61～7.48(6H,m)；7.46～7.38(5H,m)；7.21～7.18(1H,m)；7.01～6.99(1H,d)。 Referring to the synthesis method in the fourth step of Example 1, only Int-3 in the fourth step of Example 1 was replaced by Int-5 to prepare compound C500, white solid, yield: 88%, after vacuum sublimation, HPLC: 99.96 %, MS (MALDI-TOF): m/z=608.2308[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.81 (1H, s); 8.50 (1H, s); 8.25～8.18 (4H, m); 8.16～8.13(1H,m); 7.92～7.90(1H,d); 7.75～7.64(8H,m); 7.61～7.48(6H,m); 7.46～7.38(5H,m); 7.21～ 7.18(1H,m); 7.01~6.99(1H,d).
参照上述类似的合成方法，制备以下表4所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 4 were prepared:
表4Table 4
Figure PCTCN2022140610-appb-000027
Figure PCTCN2022140610-appb-000027
Figure PCTCN2022140610-appb-000028
Figure PCTCN2022140610-appb-000028
实施例3Example 3
化合物C580的制备方法，包括以下步骤：The preparation method of compound C580 comprises the following steps:
第一步：化合物Int-6的制备The first step: preparation of compound Int-6
Figure PCTCN2022140610-appb-000029
Figure PCTCN2022140610-appb-000029
20.0mmol的C-4溶解于50mL的DMF中，在氮气保护下，加入24.0mmol的联硼酸频那醇酯、30.0mmol的无水醋酸钾、0.1mmol的PdCl 2(dppf)催化剂，2.0mmol的碘化亚铜，升温至100℃，搅拌反应12小时，降到室温，加入50mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体Int-6，收率82％。 20.0mmol of C-4 was dissolved in 50mL of DMF, under nitrogen protection, 24.0mmol of diboronic acid pinacol ester, 30.0mmol of anhydrous potassium acetate, 0.1mmol of PdCl 2 (dppf) catalyst, 2.0mmol of Cuprous iodide, heat up to 100°C, stir and react for 12 hours, cool down to room temperature, add 50mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, filter, concentrate the filtrate to dryness under reduced pressure, separate and purify with a silica gel column , Int-6 was obtained as a white solid with a yield of 82%.
第二步：化合物C580的制备The second step: the preparation of compound C580
Figure PCTCN2022140610-appb-000030
Figure PCTCN2022140610-appb-000030
12.0mmol的Int-6溶解于40mL的甲苯中，在氮气保护下，加入10.0mmol的2-氯-4-苯基-6-联苯基-1,3,5-三嗪、36.0mmol的无水碳酸钠、0.01mmol的Pd132催化剂，再加入20mL的乙醇和20mL的水，升温至回流搅拌反应10小时，降到室温，加入50mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到白色固体C580，收率82％，真空升华后，HPLC：99.95％，MS(MALDI-TOF)： m/z＝674.2534[M+H] +； 1HNMR(δ、CDCl 3)：9.06(1H,s)；8.93(1H,s)；8.50(1H,s)；8.35～8.32(2H,m)；8.17～8.14(1H,m)；7.96～7.92(2H,m)；7.74～7.68(5H,m)；7.57～7.54(2H,m)；7.52～7.47(4H,m)；7.45～7.36(5H,m)；7.26～7.17(5H,m)；7.16～7.08(2H,m)。 12.0mmol of Int-6 was dissolved in 40mL of toluene, under nitrogen protection, 10.0mmol of 2-chloro-4-phenyl-6-biphenyl-1,3,5-triazine, 36.0mmol of Water sodium carbonate, 0.01mmol of Pd132 catalyst, then add 20mL of ethanol and 20mL of water, heat up to reflux and stir for 10 hours, drop to room temperature, add 50mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, Filtration, the filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain white solid C580, the yield was 82%, after vacuum sublimation, HPLC: 99.95%, MS (MALDI-TOF): m/z=674.2534[M+H] + ; 1 HNMR (δ, CDCl 3 ): 9.06(1H,s); 8.93(1H,s); 8.50(1H,s); 8.35～8.32(2H,m); 8.17～8.14(1H,m); 7.96～7.92(2H,m); 7.74～7.68(5H,m); 7.57～7.54(2H,m); 7.52～7.47(4H,m); 7.45～7.36(5H,m); 7.26～7.17(5H ,m); 7.16～7.08(2H,m).
参照上述类似的合成方法，制备以下表5所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 5 were prepared:
表5table 5
Figure PCTCN2022140610-appb-000031
Figure PCTCN2022140610-appb-000031
实施例4Example 4
化合物C491的制备：Preparation of compound C491:
Figure PCTCN2022140610-appb-000032
Figure PCTCN2022140610-appb-000032
12.0mmol的C-1溶解于60mL的二甲苯中，在氮气保护下，加入10.0mmol的二芳基胺、18.0mmol的叔丁醇钠、0.1mmol的碘化亚铜、0.1mmol的Pd 2(dba) 3催化剂，再加入0.2mmol的Xantphos，升温至110℃搅拌反应16小时，降到室温，加入20mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物C491。 12.0 mmol of C-1 was dissolved in 60 mL of xylene, and under nitrogen protection, 10.0 mmol of diarylamine, 18.0 mmol of sodium tert-butoxide, 0.1 mmol of cuprous iodide, and 0.1 mmol of Pd 2 ( dba) 3 catalyst, then add 0.2mmol of Xantphos, heat up to 110°C and stir the reaction for 16 hours, drop to room temperature, add 20mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, filter, and concentrate the filtrate to dryness under reduced pressure , separated and purified by silica gel column to obtain compound C491.
T 3为CMe 2，收率82％，真空升华后，HPLC：99.94％，MS(MALDI-TOF)：m/z＝726.3171[M+H] +； 1HNMR(δ、CDCl 3)：8.32～8.26(2H,t)；8.11～8.07(1H,d)；7.94～7.90(2H,m)；7.72～7.61(4H,m)；7.55～7.42(8H,m)；7.38～7.27(6H,m)；7.22～7.17(3H,m)；7.15～7.08(4H,m)；7.02～6.96(3H,m)；1.68(6H,s)。 T 3 is CMe 2 , yield 82%, after vacuum sublimation, HPLC: 99.94%, MS (MALDI-TOF): m/z=726.3171[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.32～ 8.26(2H,t); 8.11～8.07(1H,d); 7.94～7.90(2H,m); 7.72～7.61(4H,m); 7.55～7.42(8H,m); 7.38～7.27(6H,m ); 7.22～7.17(3H,m); 7.15～7.08(4H,m); 7.02～6.96(3H,m); 1.68(6H,s).
T 3为O，收率83％，真空升华后，HPLC：99.95％，MS(MALDI-TOF)：m/z＝700.2654[M+H] +； 1HNMR(δ、CDCl 3)：8.32～8.29(1H,d)；8.11～8.07(1H,d)；7.97～7.94(1H,d)；7.90～7.87(1H,m)；7.72～7.62(7H,m)；7.55～7.44(7H,m)；7.39～7.32(5H,m)；7.26～7.17(5H,m)；7.15～7.08(4H,m)；6.91～6.89(1H,d)。 T 3 is O, yield 83%, after vacuum sublimation, HPLC: 99.95%, MS (MALDI-TOF): m/z=700.2654[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.32～8.29 (1H,d); 8.11～8.07(1H,d); 7.97～7.94(1H,d); 7.90～7.87(1H,m); 7.72～7.62(7H,m); 7.55～7.44(7H,m) ; 7.39~7.32(5H,m); 7.26~7.17(5H,m); 7.15~7.08(4H,m); 6.91~6.89(1H,d).
参照上述类似的合成方法，制备以下表6所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 6 were prepared:
表6Table 6
Figure PCTCN2022140610-appb-000033
Figure PCTCN2022140610-appb-000033
Figure PCTCN2022140610-appb-000034
Figure PCTCN2022140610-appb-000034
Figure PCTCN2022140610-appb-000035
Figure PCTCN2022140610-appb-000035
Figure PCTCN2022140610-appb-000036
Figure PCTCN2022140610-appb-000036
实施例5Example 5
化合物C540的制备方法，包括如下步骤：The preparation method of compound C540, comprises the steps:
第一步：化合物Int-20的制备The first step: preparation of compound Int-20
Figure PCTCN2022140610-appb-000037
Figure PCTCN2022140610-appb-000037
参照实施例1第二步的合成方法，仅将Int-1替换为Int-0(实施例1的方法制备)，将实施例1第二步中的苯硼酸替换为间甲氧基苯硼酸，制备化合物Int-20，黄色固体，收率93％。With reference to the synthetic method of the second step of Example 1, only Int-1 is replaced by Int-0 (prepared by the method of Example 1), and the phenylboronic acid in the second step of Example 1 is replaced by m-methoxyphenylboronic acid, Compound Int-20 was prepared as a yellow solid with a yield of 93%.
第二步：化合物Int-21的制备The second step: the preparation of compound Int-21
Figure PCTCN2022140610-appb-000038
Figure PCTCN2022140610-appb-000038
在氮气保护下，20.0mmol的Int-20溶于100mL的醋酸中，滴加入2mL的浓硫酸，升温至回流，搅拌反应2小时，降到室温，减压浓缩干，滴加入150mL的5％氢氧化钠水溶液，用二氯甲烷萃取，有机相干燥，减压浓缩干，用硅胶柱分离纯化，得化合物Int-21，白色固体，收率：78％。Under the protection of nitrogen, 20.0 mmol of Int-20 was dissolved in 100 mL of acetic acid, 2 mL of concentrated sulfuric acid was added dropwise, the temperature was raised to reflux, the reaction was stirred for 2 hours, cooled to room temperature, concentrated to dryness under reduced pressure, and 150 mL of 5% hydrogen was added dropwise Sodium oxide aqueous solution was extracted with dichloromethane, the organic phase was dried, concentrated under reduced pressure to dryness, separated and purified by silica gel column to obtain compound Int-21 as a white solid, yield: 78%.
第三步：化合物Int-22的制备The third step: preparation of compound Int-22
Figure PCTCN2022140610-appb-000039
Figure PCTCN2022140610-appb-000039
在氮气保护下，20.0mmol的Int-21溶于80mL干燥的二氯甲烷中，降温至0℃，滴加入24.0mol的三溴化硼，搅拌反应1小时，升到室温，加入100mL饱和的碳酸钠水溶液，分出有机相，干燥，减压浓缩干，用硅胶柱分离纯化，得化合物Int-22，白色固体，收率：100％。Under nitrogen protection, 20.0 mmol of Int-21 was dissolved in 80 mL of dry dichloromethane, cooled to 0°C, 24.0 mol of boron tribromide was added dropwise, stirred for 1 hour, raised to room temperature, and 100 mL of saturated carbonic acid was added Sodium aqueous solution, the organic phase was separated, dried, concentrated under reduced pressure to dryness, separated and purified by silica gel column to obtain compound Int-22 as a white solid, yield: 100%.
第四步：化合物Int-23的制备Step 4: Preparation of Compound Int-23
Figure PCTCN2022140610-appb-000040
Figure PCTCN2022140610-appb-000040
在氮气保护下，15.0mmol的Int-22溶于50mL干燥的二氯甲烷中，加入22.5mmol的吡啶，降温至0℃，滴加入18.0mol的三氟甲磺酸酐，搅拌反应1小时，升到室温，加入50mL的2N稀盐酸，分出有机相，干燥，减压浓缩干，用硅胶柱分离纯化，得化合物Int-23，白色固体，收率：96％。Under nitrogen protection, 15.0 mmol of Int-22 was dissolved in 50 mL of dry dichloromethane, 22.5 mmol of pyridine was added, the temperature was lowered to 0°C, 18.0 mol of trifluoromethanesulfonic anhydride was added dropwise, the reaction was stirred for 1 hour, and raised to At room temperature, 50 mL of 2N dilute hydrochloric acid was added, the organic phase was separated, dried, concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain compound Int-23 as a white solid, yield: 96%.
第五步：化合物Int-24的制备Step 5: Preparation of Compound Int-24
Figure PCTCN2022140610-appb-000041
Figure PCTCN2022140610-appb-000041
参照实施例3第一步的合成方法，仅将实施例3第一步中的C-4替换为Int-23，制备化合物Int-24，白色固体，收率：86％。Referring to the synthesis method in the first step of Example 3, only C-4 in the first step of Example 3 was replaced with Int-23 to prepare compound Int-24, a white solid, with a yield of 86%.
第六步：化合物C540的制备Step 6: Preparation of compound C540
Figure PCTCN2022140610-appb-000042
Figure PCTCN2022140610-appb-000042
参照实施例3第二步的合成方法，仅将实施例3第二步中的Int-6替换为Int-24，将2-氯-4-苯基-6-联苯基-1,3,5-三嗪替换为2-氯-4,6-二苯基-1,3,5-三嗪制备化合物C540，白色固体，收率：84％,真空升华后，HPLC：99.89％，MS(MALDI-TOF)：m/z＝598.2291[M+H] +； 1HNMR(δ、CDCl 3)：8.81～8.77(4H,m)；8.45～8.42(1H,m)；8.15～8.08(3H,m)；7.92(1H,s)；7.56～7.49(5H,m)；7.46～7.37(8H,m)；7.26～7.17(4H,m)；7.02～6.97(1H,m)。 With reference to the synthetic method of the second step of Example 3, only Int-6 in the second step of Example 3 is replaced by Int-24, and 2-chloro-4-phenyl-6-biphenyl-1,3, 5-triazine was replaced by 2-chloro-4,6-diphenyl-1,3,5-triazine to prepare compound C540, white solid, yield: 84%, after vacuum sublimation, HPLC: 99.89%, MS ( MALDI-TOF): m/z＝598.2291[M+H] + ; 1 HNMR (δ, CDCl 3 ): 8.81～8.77(4H,m); 8.45～8.42(1H,m); 8.15～8.08(3H, m); 7.92(1H,s); 7.56～7.49(5H,m); 7.46～7.37(8H,m); 7.26～7.17(4H,m); 7.02～6.97(1H,m).
参照上述类似的合成方法，制备以下表7所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 7 were prepared:
表7Table 7
Figure PCTCN2022140610-appb-000043
Figure PCTCN2022140610-appb-000043
Figure PCTCN2022140610-appb-000044
Figure PCTCN2022140610-appb-000044
实施例6Example 6
化合物C525的制备：Preparation of compound C525:
Figure PCTCN2022140610-appb-000045
Figure PCTCN2022140610-appb-000045
12.0mmol的Int-23溶解于50mL的二甲苯中，在氮气保护下，加入10.0mmol的二([1,1'-联苯]-4-基)胺、18.0mmol的叔丁醇钠、0.1mmol的Pd 2(dba) 3催化剂，再加入0.2mmol的Xphos，升温至100℃搅拌反应12小时，降到室温，加入20mL的水稀释，用乙酸乙酯萃取，收集有机相，干燥，过滤，滤液减压浓缩干，用硅胶柱分离纯化，得到化合物C525，收率84％，真空升华后，HPLC：99.97％，MS(MALDI-TOF)：m/z＝686.2788[M+H] +； 1HNMR(δ、CDCl 3)：8.52～8.49(1H,m)；8.24～8.21(2H,m)；7.92～7.89(1H,m)；7.74～7.66(6H,m)；7.54～7.45(10H,m)；7.42～7.35(7H,m)；7.33～7.24(5H,m)；7.16～7.12(2H,m)；7.07～7.02(1H,m)。 12.0 mmol of Int-23 was dissolved in 50 mL of xylene, and under nitrogen protection, 10.0 mmol of bis([1,1'-biphenyl]-4-yl)amine, 18.0 mmol of sodium tert-butoxide, 0.1 1 mmol of Pd 2 (dba) 3 catalyst, then add 0.2 mmol of Xphos, heat up to 100 ° C and stir for 12 hours, drop to room temperature, add 20 mL of water to dilute, extract with ethyl acetate, collect the organic phase, dry, filter, The filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain compound C525 with a yield of 84%, after vacuum sublimation, HPLC: 99.97%, MS (MALDI-TOF): m/z=686.2788[M+H] + ; 1 HNMR(δ, CDCl 3 ): 8.52～8.49(1H,m); 8.24～8.21(2H,m); 7.92～7.89(1H,m); 7.74～7.66(6H,m); 7.54～7.45(10H, m); 7.42～7.35(7H,m); 7.33～7.24(5H,m); 7.16～7.12(2H,m); 7.07～7.02(1H,m).
参照上述类似的合成方法，制备以下表8所示化合物：With reference to the above-mentioned similar synthetic methods, the compounds shown in the following table 8 were prepared:
表8Table 8
Figure PCTCN2022140610-appb-000046
Figure PCTCN2022140610-appb-000046
Figure PCTCN2022140610-appb-000047
Figure PCTCN2022140610-appb-000047
实施例7Example 7
一种有机电致发光元件200，其结构如图2所示，包括基板101、设于基板101上的阳极层102、设于阳极层102上的空穴注入层103、设于空穴注入层103上的空穴传输层104、设于空穴传输层104上的电子阻挡层105、设于电子阻挡层105上的发光层106、设于发光层106上的电子传输层107、设于电子传输层107上的电子注入层108、设于电子注入层108上的阴极层109，以及设于阴极层之上的CPL层110，其制备方法包括如下步骤：A kind of organic electroluminescent element 200, its structure is shown in Figure 2, comprises substrate 101, is arranged on the anode layer 102 on the substrate 101, is arranged on the hole injection layer 103 on the anode layer 102, is arranged on the hole injection layer The hole transport layer 104 on the hole transport layer 103, the electron blocking layer 105 on the hole transport layer 104, the light emitting layer 106 on the electron blocking layer 105, the electron transport layer 107 on the light emitting layer 106, the electron The electron injection layer 108 on the transport layer 107, the cathode layer 109 arranged on the electron injection layer 108, and the CPL layer 110 arranged on the cathode layer, its preparation method comprises the following steps:
1)将涂布了ITO导电层的玻璃基片在清洗剂中超声处理30分钟，在去离子水中冲洗，在丙酮/乙醇混合溶剂中超声30分钟，在洁净的环境下烘烤至完全干燥，用紫外光清洗机照射10分钟，并用低能阳离子束轰击表面。1) The glass substrate coated with the ITO conductive layer is ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in acetone/ethanol mixed solvent for 30 minutes, and baked in a clean environment until completely dry, Irradiate with a UV light cleaner for 10 minutes and bombard the surface with a low-energy positive ion beam.
2)把上述处理好的ITO玻璃基片置于真空腔内，抽真空至1×10 -5～9×10 -3Pa，在上述ITO膜上蒸镀金属铝作为阳极层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000048
蒸镀化合物HI01作为空穴注入层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000049
2) Place the above-mentioned treated ITO glass substrate in a vacuum chamber, vacuumize to 1×10 -5 ~ 9×10 -3 Pa, evaporate metal aluminum on the above-mentioned ITO film as the anode layer, and the thickness of the evaporated film is
Figure PCTCN2022140610-appb-000048
The evaporated compound HI01 was used as the hole injection layer, and the evaporated film thickness was
Figure PCTCN2022140610-appb-000049
3)在上述空穴注入层上继续蒸镀化合物HTM为空穴传输层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000050
3) Continue to vapor-deposit the compound HTM on the above-mentioned hole-injection layer as the hole-transport layer, and the vapor-deposited film thickness is
Figure PCTCN2022140610-appb-000050
4)在上述空穴传输层上继续蒸镀本发明式(I)所示的化合物为电子阻挡层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000051
4) On the above-mentioned hole transport layer, continue to vapor-deposit the compound shown in the formula (I) of the present invention as an electron blocking layer, and the vapor-deposited film thickness is
Figure PCTCN2022140610-appb-000051
5)在电子阻挡层上继续蒸镀PHT为主体材料和GD016为掺杂材料，GD016为PHT质量的5％，作为有机发光层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000052
5) Continue to vapor-deposit PHT on the electron blocking layer as the host material and GD016 as the dopant material, and GD016 is 5% of the mass of PHT. As an organic light-emitting layer, the vapor-deposited film thickness is
Figure PCTCN2022140610-appb-000052
6)在有机发光层上继续蒸镀一层LiQ和ET06作为电子传输层，LiQ和ET06的质量比为50:50，蒸镀膜厚为
Figure PCTCN2022140610-appb-000053
6) Continue to vapor-deposit a layer of LiQ and ET06 on the organic light-emitting layer as the electron transport layer. The mass ratio of LiQ and ET06 is 50:50, and the thickness of the vapor-deposited film is
Figure PCTCN2022140610-appb-000053
7)在电子传输层之上继续蒸镀一层LiF为电子注入层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000054
7) Continue to evaporate a layer of LiF on the electron transport layer as the electron injection layer, and the thickness of the evaporated film is
Figure PCTCN2022140610-appb-000054
8)在电子注入层之上蒸镀金属镁和银作为透明阴极层，镁和银的质量比为1:2，蒸镀膜厚为
Figure PCTCN2022140610-appb-000055
8) Metal magnesium and silver are vapor-deposited on the electron injection layer as a transparent cathode layer, the mass ratio of magnesium and silver is 1:2, and the thickness of the vapor-deposited film is
Figure PCTCN2022140610-appb-000055
9)在透明阴极层之上再蒸镀一层NPB作为元件的CPL层，蒸镀膜厚为
Figure PCTCN2022140610-appb-000056
得到本发明提供的OLED元件。 9) On the transparent cathode layer, another layer of NPB is vapor-deposited as the CPL layer of the element, and the thickness of the vapor-deposited film is
Figure PCTCN2022140610-appb-000056
Obtain the OLED element provided by the present invention.
实施例7中使用的化合物HI01、HTM、PHT、GD016、ET06和LiQ的结构如下：The structures of the compounds HI01, HTM, PHT, GD016, ET06 and LiQ used in Example 7 are as follows:
Figure PCTCN2022140610-appb-000057
Figure PCTCN2022140610-appb-000057
实施例8Example 8
一种有机电致发光元件100，其结构如图1所示，包括基板101、设于基板101上的阳极层102、设于阳极层102上的空穴注入层103、设于空穴注入层103上的空穴传输层104、设于空穴传输层104上的电子阻挡层105、设于电子阻挡层105上的发光层106、设于发光层106上的空穴阻挡层107、设于空穴阻挡层107上的电子传输层108、设于电子传输层108上的电子注入层109、设于电子注入层109上的阴极层110，以及设于阴极层110之上的CPL层111。A kind of organic electroluminescent element 100, its structure is shown in Figure 1, comprises substrate 101, is arranged on the anode layer 102 on the substrate 101, is arranged on the hole injection layer 103 on the anode layer 102, is arranged on the hole injection layer The hole transport layer 104 on the hole transport layer 103, the electron blocking layer 105 on the hole transport layer 104, the light emitting layer 106 on the electron blocking layer 105, the hole blocking layer 107 on the light emitting layer 106, the The electron transport layer 108 on the hole blocking layer 107 , the electron injection layer 109 on the electron transport layer 108 , the cathode layer 110 on the electron injection layer 109 , and the CPL layer 111 on the cathode layer 110 .
对比例1Comparative example 1
按照与实施例7相同的步骤，将步骤4)中的式(I)所示的化合物替换为B-1，得到对比元件1；B-1结构式如下：According to the same steps as in Example 7, the compound shown in the formula (I) in step 4) is replaced by B-1 to obtain comparative element 1; the structural formula of B-1 is as follows:
Figure PCTCN2022140610-appb-000058
Figure PCTCN2022140610-appb-000058
对比例2Comparative example 2
按照与实施例7相同的步骤，将步骤4)中的式(I)所示的化合物替换为B-2，得到对比元件2；B-2结构式如下：According to the same steps as in Example 7, the compound shown in the formula (I) in step 4) is replaced by B-2 to obtain comparative element 2; the structural formula of B-2 is as follows:
Figure PCTCN2022140610-appb-000059
Figure PCTCN2022140610-appb-000059
对比例3Comparative example 3
按照与实施例7相同的步骤，将步骤4)中的式(I)所示的化合物替换为B-3，得到对比元件3；B-3结构式如下：According to the same steps as in Example 7, the compound shown in the formula (I) in step 4) is replaced by B-3 to obtain comparative element 3; the structural formula of B-3 is as follows:
Figure PCTCN2022140610-appb-000060
Figure PCTCN2022140610-appb-000060
所得元件的性能检测数据以对比元件1为基准进行归一化处理，其结果列于表9中，其中驱动电压、发光效率和半峰宽(FWHM)是在元件的电流密度为10mA/cm 2条件下得出，元件 的LT95％寿命是在电流密度为50mA/cm 2的起始条件下测得。 The performance detection data of the obtained element is normalized with reference to the comparative element 1, and the results are listed in Table 9, wherein the driving voltage, luminous efficiency and half-maximum width (FWHM) are obtained when the current density of the element is 10mA/cm 2 The LT95% lifetime of the component is measured under the initial condition of a current density of 50mA/cm 2 .
表9 各元件性能检测结果Table 9 Performance test results of each component
Figure PCTCN2022140610-appb-000061
Figure PCTCN2022140610-appb-000061
由表9可知，本发明的芴衍生物作为电子阻挡材料制备成的发光元件同样在10mA/cm 2条件下，驱动电压相较B-1、B-2、B-3降低，尤其是化合物C555(T 3为CMe 2)发光效率有显著提高，而且在电流密度为50mA/cm 2起始条件下的LT95％寿命有明显优势。 It can be seen from Table 9 that the light-emitting element prepared by using the fluorene derivative of the present invention as an electron-blocking material also has a lower driving voltage than B-1, B-2, and B-3 under the condition of 10mA/cm 2 , especially compound C555 (T 3 is CMe 2 ) The luminous efficiency is significantly improved, and the LT95% lifetime under the initial condition of the current density of 50mA/cm 2 has obvious advantages.
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail with general descriptions and specific embodiments above, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

  1. 一种芴衍生物，其特征在于，其结构式如式(I)所示：A fluorene derivative, characterized in that its structural formula is as shown in formula (I):
    Figure PCTCN2022140610-appb-100001
    Figure PCTCN2022140610-appb-100001
    其中，in,
    Ar 1选自由C 1-C 40的烷基、C 3-C 40的环烷基或带有支链的烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 1 is selected from C 1 -C 40 alkyl, C 3 -C 40 cycloalkyl or branched alkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C A group consisting of 6 -C 60 fused ring aryl, substituted or unsubstituted C 6 -C 60 arylamino, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl;
    Z各自独立地选自CR 10或N； Each Z is independently selected from CR 10 or N;
    R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自由氢、氘、卤素、腈基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 2-C 60杂环芳基或式(II)组成的群组，任意相邻的两个或多个基团可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted C 6 -C 60 fused ring aryl, substituted or unsubstituted C 2 -C 60 heterocyclic aryl or a group consisting of formula (II), any adjacent two One or more groups may optionally be joined or fused to form additional one or more substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S;
    式(II)的结构式如下：The structural formula of formula (II) is as follows:
    Figure PCTCN2022140610-appb-100002
    Figure PCTCN2022140610-appb-100002
    Ar 2、Ar 3各自独立地选自由取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted C 6 -C 60 aryl groups, substituted or unsubstituted C 6 -C 60 condensed ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamines group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    m选自0～5的整数；m is an integer selected from 0 to 5;
    L选自单键、取代或未取代的C 6-C 60的亚芳基、或者取代或未取代的C 2-C 60亚杂芳基； L is selected from a single bond, a substituted or unsubstituted C 6 -C 60 arylene group, or a substituted or unsubstituted C 2 -C 60 heteroarylene group;
    *—表示式(II)与式(I)的连接键。*—represents the link between formula (II) and formula (I).
  2. 根据权利要求1所述的芴衍生物，其特征在于，Ar 1选自由甲基、乙基、环戊基、环己基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； The fluorene derivative according to claim 1 , wherein Ar is selected from methyl, ethyl, cyclopentyl, cyclohexyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    Ar 2、Ar 3各自独立地选自由取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Ar 2 and Ar 3 are each independently selected from a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 arylamino group, or a substituted or unsubstituted C 2 -C 60 heterocycle A group consisting of aryl groups;
    Z选自CR 10； Z is selected from CR 10 ;
    R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10各自独立地选自由氢、氘、取代或未取代的C 6-C 60芳基、取代或未取代的C 2-C 60杂环芳基或式(II)组成的群组； R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C 6 -C 60 aryl , a substituted or unsubstituted C 2 -C 60 heterocyclic aryl group or a group consisting of formula (II);
    m选自0、1或2。m is selected from 0, 1 or 2.
  3. 根据权利要求1或2所述的芴衍生物，其特征在于，所述C 2-C 60杂环芳基选自由以下II-1～II-17所示基团组成的群组： The fluorene derivative according to claim 1 or 2, wherein the C 2 -C 60 heterocyclic aryl group is selected from the group consisting of the following groups shown in II-1 to II-17:
    Figure PCTCN2022140610-appb-100003
    Figure PCTCN2022140610-appb-100003
    Figure PCTCN2022140610-appb-100004
    Figure PCTCN2022140610-appb-100004
    其中，in,
    Z 1、Z 2各自独立地选自由氢、氘、卤素、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1-C 60烷基、C 2-C 60烯基、C 2-C 60炔基、C 1-C 60烷氧基、C 3-C 60环烷烃基、C 3-C 60环烯烃基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Z 1 and Z 2 are each independently selected from hydrogen, deuterium, halogen, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid group or sulfonate thereof , phosphate or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 6 -C 60 arylsulfide group , or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    x1表示1-4的整数；x2表示1-3的整数；x3表示1或2；x4表示1-6的整数；x5表示1-5的整数；x1 represents an integer of 1-4; x2 represents an integer of 1-3; x3 represents an integer of 1 or 2; x4 represents an integer of 1-6; x5 represents an integer of 1-5;
    T 1表示O、S、CR’R”或NAr’； T 1 means O, S, CR'R" or NAr';
    R’、R”各自独立地选自由氢、氘、C 1-C 60的烷基、C 1-C 60的杂烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
    Ar’选自由C 1-C 60的烷基、C 1-C 60的杂烷基、C 3-C 60的环烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
    Figure PCTCN2022140610-appb-100005
    表示取代基与主体结构的连接键。
    Figure PCTCN2022140610-appb-100005
    Indicates the link between the substituent and the main structure.
  4. 根据权利要求1-3任一项所述的芴衍生物，其特征在于，所述L选自单键或由以下III-1～III-15所示基团组成的群组：The fluorene derivative according to any one of claims 1-3, wherein said L is selected from a single bond or a group consisting of the following groups shown in III-1 to III-15:
    Figure PCTCN2022140610-appb-100006
    Figure PCTCN2022140610-appb-100006
    其中，in,
    Z 11、Z 12各自独立地选自由氢、氘、卤原子、羟基、腈基、硝基、氨基、脒基、肼基、腙基、羧基或其羧酸盐、磺酸基或其磺酸盐、磷酸基或其磷酸盐、C 1-C 60的烷基、C 2-C 60的烯基、C 2-C 60的炔基、C 1-C 60的烷氧基、C 3-C 60的环烷烃基、C 3-C 60的环烯烃基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基组成的群组； Z 11 and Z 12 are each independently selected from hydrogen, deuterium, halogen atom, hydroxyl, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or its carboxylate, sulfonic acid or its sulfonic acid Salt, phosphate group or its phosphate, C 1 -C 60 alkyl, C 2 -C 60 alkenyl, C 2 -C 60 alkynyl, C 1 -C 60 alkoxy, C 3 -C 60 cycloalkane group, C 3 -C 60 cycloalkene group, substituted or unsubstituted C 6 -C 60 aryl group, substituted or unsubstituted C 6 -C 60 aryloxy group, substituted or unsubstituted C 60 -C 60 aryl sulfide group, or a group consisting of substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups;
    Z 13表示取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳氧基、取代或未取代的C 6-C 60芳硫醚基、或者取代或未取代的C 2-C 60杂环芳基中的一种或多种； Z 13 represents a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 6 -C 60 arylsulfide group, or a substituted or unsubstituted One or more of the C 2 -C 60 heterocyclic aryl groups;
    y1表示1-4的整数；y2表示1-6的整数；y3表示1-3的整数；y4表示1-5的整数；y1 represents an integer of 1-4; y2 represents an integer of 1-6; y3 represents an integer of 1-3; y4 represents an integer of 1-5;
    T 2表示O、S、CR’R”或NAr’； T 2 represents O, S, CR'R" or NAr';
    R’、R”各自独立地选自由氢、氘、C 1-C 60的烷基、C 1-C 60的杂烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组，R’和R”可任选地接合或稠合形成另外的一个或多个取代或未取代的环，在所形成的环中含有或不含有一个或多个杂原子N、P、B、O或S；优选地，R’、R”为甲基、苯基或芴基； R', R" are each independently selected from hydrogen, deuterium, C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups, R' and R" can be optionally joined or fused to form another one or more Substituted or unsubstituted rings, with or without one or more heteroatoms N, P, B, O or S in the ring formed; preferably, R', R" are methyl, phenyl or fluorenyl ;
    Ar’选自由C 1-C 60的烷基、C 1-C 60的杂烷基、C 3-C 60的环烷基、取代或未取代的C 6-C 60芳基、取代或未取代的C 6-C 60稠环芳基、取代或未取代的C 6-C 60芳胺基、或者取代或未取代的C 2-C 60杂环芳基组成的群组；优选地，Ar’为甲基、乙基、苯基或萘基； Ar' is selected from C 1 -C 60 alkyl, C 1 -C 60 heteroalkyl, C 3 -C 60 cycloalkyl, substituted or unsubstituted C 6 -C 60 aryl, substituted or unsubstituted A group consisting of C 6 -C 60 fused ring aryl groups, substituted or unsubstituted C 6 -C 60 arylamino groups, or substituted or unsubstituted C 2 -C 60 heterocyclic aryl groups; preferably, Ar' is methyl, ethyl, phenyl or naphthyl;
    Figure PCTCN2022140610-appb-100007
    表示取代基与主体结构的连接键。
    Figure PCTCN2022140610-appb-100007
    Indicates the link between the substituent and the main structure.
  5. 根据权利要求1-4任一项所述的芴衍生物，其特征在于，所述芴衍生物的结构式选自由以下C473至C583组成的群组：The fluorene derivative according to any one of claims 1-4, wherein the structural formula of the fluorene derivative is selected from the group consisting of the following C473 to C583:
    Figure PCTCN2022140610-appb-100008
    Figure PCTCN2022140610-appb-100008
    Figure PCTCN2022140610-appb-100009
    Figure PCTCN2022140610-appb-100009
    Figure PCTCN2022140610-appb-100010
    Figure PCTCN2022140610-appb-100010
    Figure PCTCN2022140610-appb-100011
    Figure PCTCN2022140610-appb-100011
    Figure PCTCN2022140610-appb-100012
    Figure PCTCN2022140610-appb-100012
    Figure PCTCN2022140610-appb-100013
    Figure PCTCN2022140610-appb-100013
    其中，*—T 3—*选自*—O—*、*—S—*或下述结构中的一种： Wherein, *—T 3 —* is selected from *—O—*, *—S—* or one of the following structures:
    Figure PCTCN2022140610-appb-100014
    Figure PCTCN2022140610-appb-100014
    *—和—*表示连接键。*— and —* indicate connecting keys.
  6. 一种有机电致发光材料，其特征在于，其原料包括权利要求1-5任一项所述的芴衍生物。An organic electroluminescent material, characterized in that its raw material comprises the fluorene derivative described in any one of claims 1-5.
  7. 权利要求1-5任一项所述的芴衍生物在制备有机电致发光元件中的应用。The use of the fluorene derivative described in any one of claims 1-5 in the preparation of organic electroluminescent elements.
  8. 一种有机电致发光元件，其特征在于，其包括：第一电极、第二电极、CPL层和置于所述第一电极、所述第二电极之间的一层以上的有机层；所述有机层、CPL层中的至少一层包括权利要求1-5任一项所述的芴衍生物。An organic electroluminescent element, characterized in that it comprises: a first electrode, a second electrode, a CPL layer, and more than one organic layer placed between the first electrode and the second electrode; At least one of the organic layer and the CPL layer comprises the fluorene derivative according to any one of claims 1-5.
  9. 根据权利要求8所述的有机电致发光元件，其特征在于，所述有机层包括空穴注入层、空穴传输层、空穴阻挡层、发光层、电子传输层、电子注入层、CPL层或电子阻挡层。The organic electroluminescent element according to claim 8, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a CPL layer or electron blocking layer.
  10. 一种消费型产品，其特征在于，其包括权利要求8或9所述的有机电致发光元件。A consumer product, characterized in that it comprises the organic electroluminescence element described in claim 8 or 9.
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