WO2020169060A1 - 含螺二芴结构的有机化合物及其应用 - Google Patents

含螺二芴结构的有机化合物及其应用 Download PDF

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WO2020169060A1
WO2020169060A1 PCT/CN2020/075971 CN2020075971W WO2020169060A1 WO 2020169060 A1 WO2020169060 A1 WO 2020169060A1 CN 2020075971 W CN2020075971 W CN 2020075971W WO 2020169060 A1 WO2020169060 A1 WO 2020169060A1
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钱晓春
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常州强力电子新材料股份有限公司
常州强力昱镭光电材料有限公司
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Definitions

  • the invention belongs to the technical field of organic electroluminescence (organic EL, also known as OLED), and specifically relates to an organic compound containing a spirobifluorene structure that can be used in OLED devices, and its application in OLED devices, and also relates to The organic compound OLED device.
  • organic EL organic electroluminescence
  • OLED organic electroluminescence
  • OLED devices have the advantages of self-luminescence, high contrast, good color saturation, wide viewing angle, fast response speed and rollability, and are currently recognized as the most promising new generation of display technology.
  • Inorganic optoelectronic materials are blocks composed of rigid metals, metalloids, and semiconductor elements. They are one piece and cannot be bent. Unlike this, OLED materials are composed of organic molecules stacked to form a continuous film, with each film thickness less than 0.0001 Centimeter (ie sub-micron level), soft and bendable, can be freely applied to the Internet of Things, wearable devices, military aircraft, etc. If used in white light illumination, OLED also has the advantage of energy saving, so it is a popular member of optoelectronic materials.
  • the OLED photoelectric functional material film layer constituting the OLED device includes at least two or more layers.
  • the OLED device used in industry usually includes a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), and a light emitting layer. (EML), hole blocking layer (HBL), electron transport layer (ETL), electron injection layer (EIL) and other layers, which means that the optoelectronic functional materials of OLED devices include at least hole injection materials and hole transport Materials, luminescent materials, electron transport materials, etc.
  • the material types and matching forms of optoelectronic functional materials are characterized by richness and diversity. For OLED devices of different structures, the optoelectronic functional materials used have strong selectivity.
  • the spirobifluorene molecule has a non-planar spatial structure, and two fluorene monomers are bridged together with the sp 3 hybridized C atom as the center. Introducing it into molecules with electroluminescent properties has potential high application value for improving the thermal stability and spectral stability of the molecules.
  • the purpose of the present invention is to provide an organic compound with a spirobifluorene structure containing diarylamine substituents, which has a non-planar spatial structure, a higher glass transition temperature, suitable HOMO and LUMO energy levels, and Higher Eg can be sublimated without decomposition and residues, which can effectively improve the light-emitting performance of OLED devices and the life of OLED devices. It is suitable for phosphorescent and fluorescent (including TADF) OLED devices, especially in This is the case when using the compound as a hole injection material and/or hole transport material.
  • the organic compound of the spirobifluorene structure containing a diarylamine substituent of the present invention has a structure represented by the following chemical formula (1):
  • Rings A, B and C exist alone or at the same time, each independently represents a substituted or unsubstituted condensed aryl group or heteroaryl group with 6-18 carbon atoms on the ring;
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 each independently represent a substituted or unsubstituted aryl group or heterocyclic aryl group, and Ar 1 and Ar 2 may be connected to each other through E 1 to form a ring , Ar 3 and Ar 4 can be connected to each other through E 2 to form a ring, and Ar 5 and Ar 6 can be connected to each other through E 3 to form a ring;
  • E 1 , E 2 , and E 3 each independently represent a direct bond, O, S, CRR' or NR, wherein R and R'each independently represent a C 1 -C 8 linear or branched alkyl group, C 1- C 8 alkoxy, C 7 -C 14 aralkyl;
  • S 1 , S 2 , and S 3 each independently represent a direct bond, a substituted or unsubstituted arylene group, and a substituted or unsubstituted heteroarylene group;
  • n, and t each independently represent an integer from 0 to 3;
  • R 1 , R 2 , R 3 , and R 4 each independently represent hydrogen, deuterium, halogen, nitrile, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Substituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylaryl, substituted or unsubstituted aralkyl, A substituted or unsubstituted aralkenyl group, or a substituted or unsubstituted heterocyclic group;
  • x and y each independently represent 0 or 1, and both are not 0 at the same time.
  • rings A, B and C exist alone, that is, only A or B or C exists. It is further preferred that rings A, B and C each independently represent a benzene ring.
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 each independently have 6-60 carbon atoms, and each independently represents a substituted or unsubstituted phenyl, substituted or unsubstituted Substituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, Substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, or Substituted or unsubstituted carbazolyl.
  • S 1 , S 2 and S 3 each independently represent a direct bond, a C 6 -C 20 arylene group or a heteroarylene group. More preferably, S 1 , S 2 and S 3 represent direct bonds, that is, the spirobifluorene structure is directly connected to the N atom.
  • R 1 , R 2 , R 3 , and R 4 each independently represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2- Ethylhexyl, trifluoromethyl, pentafluoroethyl, phenyl, 1-naphthyl, 2-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, methoxy, ethoxy, N-propoxy, iso
  • S 1 , S 2 and S 3 in the structure of formula (1) are all direct bonds, and rings A, B and C exist separately as benzene ring structures. That is, the organic compound of the spirobifluorene structure of the present invention is selected from compounds of the following formulas (2)-(4):
  • R 1 , R 2 , R 3 , and R 4 all represent hydrogen, that is, the organic compound of the spirobifluorene structure of the present invention is selected from compounds of the following formulas (2-1)-(4-1):
  • the organic compound of the spirobifluorene structure of the present invention is selected from the compound of formula (2-1), and the sum of x and y is equal to 1. That is, it is preferably selected from compounds of the following formulas (2-2) and (2-3):
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 are each independently selected from the following structures:
  • R 5 each independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl , Phenyl, 4-tert-butylphenyl, cycloalkyl.
  • the raw material A is added with bromofluorenone under the action of n-butyllithium reagent to obtain intermediate alcohol B, which is cyclized to form dihalobenzospirobifluorene C after hydrolysis, which is then CN stepwise with diarylamine
  • the coupling reaction firstly obtains compound D substituted with mono-diarylamine, and then obtains the compound of formula (2-2).
  • the raw material A' is added with dihalogenated fluorenone under the action of n-butyl lithium reagent to obtain intermediate alcohol B', which is cyclized to form dihalogenated benzospirobifluorene C'after hydrolysis, and then with diarylamine
  • the CN coupling reaction is carried out step by step to obtain the monodiarylamine substituted compound D'first, and then the compound of formula (2-3).
  • Intermediate F is obtained from the reaction of methyl 1-bromo-2-naphthoate (E) with bromophenylboronic acid, which is then hydrolyzed to produce Intermediate G, which is formed into a ring to obtain Intermediate H; under the action of n-butyl lithium reagent, intermediate Form H reacts with dihalobiphenyl to obtain intermediate alcohol B", which is cyclized to form dihalobenzospirobifluorene C" after hydrolysis, and then undergoes CN coupling reaction with diarylamine step by step to obtain formula ( 2-2) Compound.
  • the intermediate dihalobenzospirobifluorene and diarylamine can be simplified for CN coupling step by step.
  • the product can be obtained by directly performing CN coupling reaction between the dihalobenzospirobifluorene and the same diarylamine.
  • the present invention also relates to the application of the above-mentioned spirobifluorene structure organic compound containing diarylamine substituent groups in OLED devices, and OLED devices containing the organic compound.
  • the OLED device includes: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the organic One or more of the material layers contains the above-mentioned organic compound of the present invention.
  • the organic material layer may be composed of a single layer structure, or may be composed of a multilayer structure in which two or more organic material layers are stacked.
  • the light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as organic material layers.
  • the device structure is not limited to this, and may include a smaller number of organic layers.
  • the organic material layer includes a hole transport layer
  • the hole transport layer includes the above-mentioned organic compound of the present invention.
  • the organic material layer includes a hole injection layer and a hole transport layer, wherein the hole transport layer includes the above-mentioned organic compound of the present invention, and the hole injection layer uses a compound HAT-CN having the following structural formula:
  • the organic material layer includes a hole injection layer, and the hole injection layer includes the above-mentioned organic compound of the present invention.
  • the hole injection layer further includes a p-type doping material doped with a doping concentration of 1-20 wt%, and the chemical structure of the p-type doping material is as follows:
  • the organic material layer includes a hole injection layer and a hole transport layer, and both the hole injection layer and the hole transport layer include the above-mentioned organic compound of the present invention.
  • the organic material layer further includes an electron blocking layer, and the electron blocking layer uses compound HT2 of the following chemical structure:
  • the organic material layer further includes a light-emitting layer, and the light-emitting layer uses compound BH as the main light-emitting body, and compound BD as the guest light-emitting body, wherein the doping ratio of the guest light-emitting body is 1-10% by weight.
  • the chemical structure is as follows:
  • the organic material layer further includes an electron transport layer, and the electron transport layer uses the compound ET of the following chemical structure, and contains lithium 8-quinolinolate (Lithium 8-quinolinolate, abbreviated as Liq) doped with 50% by weight:
  • Liq lithium 8-quinolinolate
  • the organic material layer further includes an electron injection layer, and compounds that can be used for the electron injection layer include lithium fluoride (LiF), cesium fluoride (CsF), Liq, Yb, and the like.
  • LiF lithium fluoride
  • CsF cesium fluoride
  • Liq Liq
  • Yb Yb
  • the OLED device of the present invention may be of a top emission type, a bottom emission type or a bidirectional emission type.
  • the use of the above-mentioned organic compound of the present invention in the organic material layer of an OLED device can improve the efficiency of the device, reduce the driving voltage and/or improve the life characteristics of the device. With low driving voltage and long service life, it exhibits high stability device performance.
  • Figure 1 is a schematic diagram of the structure of an OLED device in the device application performance characterization; among them,
  • the experimental device was fully dried, and methyl 1-bromo-2-naphthoate (E, 113mmo1, 30g), p-bromophenylboronic acid (114mmo1, 23g), 450mL toluene, 20mL ethanol, were added to a 1L four-necked flask under nitrogen.
  • Water 200mL, potassium carbonate (339mmo1, 47g), tetrakis(triphenylphosphonium) palladium (1mmo1, 1.2g) heated to 78°C and refluxed, stirred for 5h, and TLC followed the reaction process of the raw materials; after the reaction was completed, the heating was stopped.
  • the intermediate H2-H4 was synthesized by using different raw materials. The details are shown in Table 1 below.
  • Example H2 and H3 have the same raw materials, and two products can be obtained according to the different positions of the ring closure, and the two substances are separated by column chromatography.
  • the intermediate C3-C18 is synthesized by using different raw materials. The details are shown in Table 2 below.
  • the C-N coupling reaction is carried out step by step from the intermediate C and the diarylamine to obtain the final target compound.
  • the difference in the reactivity of different halogen substituent groups can be used to obtain the monodiarylamine substituted halogenated benzospirobifluorene, the intermediate D, through a stepwise C-N coupling reaction.
  • the intermediate D2-D10 is synthesized by using different raw materials. The details are shown in Table 3 below.
  • the experimental device was fully dried, and D1 (34.2g, 45mmol) and 12.1g (49.5mmol) of N-phenyl-4-benzidine were added to a 500mL four-necked flask under nitrogen, and then dried and degassed toluene was added as Solvent, add 6.5g (67.5mmol) sodium tert-butoxide and 0.88g (0.96mmol) catalyst Pd 2 (dba) 3 , raise the temperature to 80°C, slowly add 4.5 mL of tri-tert-butylphosphine toluene with a mass concentration of 10% The solution was heated to 100-105°C after dripping, and reacted for 6 hours.
  • the glass transition temperature Tg is measured by differential scanning calorimetry (DSC, American TA Company DSC25 Differential Scanning Calorimeter), and the heating rate is 10°C/min; the thermal weight loss temperature Td is the temperature at which weight loss is 5% in a nitrogen atmosphere.
  • the measurement was carried out on the TGA55 thermogravimetric analyzer of American TA Company, and the nitrogen flow rate was 20 mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level were measured by cyclic voltammetry.
  • the compound of the present invention has a higher glass transition temperature, which can ensure the thermal stability of the compound, so as to prevent the amorphous film of the compound from turning into a crystalline film, so that the prepared compound containing the organic compound of the present invention
  • the life span of OLED devices is improved.
  • the compounds of the present invention have different HOMO and LOMO energy levels and can be applied to different functional layers of OLED devices.
  • the organic compound of the present invention is particularly suitable for hole injection layer (HIL), hole transport layer (HTL), electron blocking layer (EBL) and/or light emitting layer in OLED devices ( EML). They can be used as a separate layer or as a mixed component in HIL, HTL, EBL or EML.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EML light emitting layer in OLED devices
  • the other materials used in the device embodiment and the comparative embodiment are all existing known products on sale, which can be purchased from the market.
  • the structural formula of the organic materials used is as follows:
  • the OLED device is manufactured.
  • the specific steps are: the glass substrate (Corning Glass 50mm*50mm*0.7mm) coated with ITO (Indium Tin Oxide) with a thickness of 130nm is ultrasonically washed with isopropanol and pure water respectively After 5 minutes, it was cleaned with ultraviolet ozone, and then the glass substrate was transferred to the vacuum deposition chamber; the hole injection material HAT-CN was thermally deposited on the transparent ITO electrode with a thickness of 5 nm (about 10 -7 Torr).
  • the host BH and 4% guest dopant BD were vacuum deposited with a thickness of 25nm; an electron transport layer containing 50% Liq (lithium quinolate) was used to form an electron transport layer with a thickness of 25nm; and finally 1nm was deposited sequentially Thick lithium fluoride (electron injection layer) and aluminum with a thickness of 100 nm form the cathode; the device is transported from the deposition chamber to the glove box, and then encapsulated with a UV curable epoxy resin and a glass cover containing a moisture absorbent.
  • the device structure is expressed as: ITO(130nm)/HAT-CN(5nm)/Compound 1-2(140nm)/HT2(10nm)/BH:BD(25nm)/ET:Liq(25nm)/LiF(1nm)/ Al (100nm).
  • the structure of the fabricated OLED light-emitting device is shown in Table 6, and the test results are shown in Table 7.
  • the deposition rates of organic materials, lithium fluoride, and aluminum were maintained at 0.1 nm/s, 0.05 nm/s, and 0.2 nm/s, respectively.
  • Example 6 The experiment was performed in the same manner as in Device Example 1, except that as the hole transport layer, Compound 1-6 was used instead of Compound 1-2 in Example 1.
  • the structure of the fabricated OLED light-emitting device is shown in Table 6, and the test results are shown in Table 7.
  • Example 6 The experiment was performed in the same manner as in Device Example 1, except that as the hole transport layer, HT1 was used instead of Compound 1-2 in Example 1.
  • the structure of the fabricated OLED light-emitting device is shown in Table 6, and the test results are shown in Table 7.
  • the luminous color is distinguished and defined by the CIE x, y chromaticity coordinates;
  • the driving voltage refers to the voltage with a brightness of 1cd/m 2 ;
  • the current efficiency refers to the luminous brightness at a unit current density;
  • the luminous efficiency refers to the power consumption per unit of electric power
  • external quantum efficiency (EQE) refers to the ratio of the number of photons emitted from the surface of the component to the number of electrons in the observation direction;
  • LT95@1000nits refers to the initial brightness of 1000nits, and the device is under constant current conditions The time for the brightness to decrease from the initial 100% to 95%.
  • the compounds used in device examples 1-5 are used as the hole transport layer in the organic light-emitting device.
  • the benzidine type material HT1 it has excellent hole transport ability and exhibits low voltage and High efficiency characteristics.
  • high triplet energy characteristic of spiro ring materials
  • the organic light-emitting device including the present invention has a low driving voltage and a long service life, and exhibits a highly stable device performance.
  • the device manufacturing processes of device embodiments 6-10 of the present invention are completely the same, and the same substrate and electrode materials are used, and the film thickness of the electrode materials is also consistent. The difference is that the device The hole injection material and hole transport material were replaced, and the hole injection layer was doped with 2wt% p-type doping material.
  • the compounds used in device examples 6-10 are used as the main material of the hole injection layer and the hole transport layer in the organic light-emitting device.
  • the hole injection layer is doped with a p-type doping compound, which is comparable to the benzidine type material. Compared with, it has excellent hole injection and transport capabilities and exhibits low voltage and high efficiency characteristics. At the same time, it also exhibits better stability and life. It can be seen that the organic light-emitting device including the present invention has a low driving voltage and a long service life, and exhibits a highly stable device performance.

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Abstract

本发明公开一种含二芳基胺取代基团的螺二芴结构的有机化合物，具有如式(1)所示的结构。该化合物具有非平面的空间结构、较高的玻璃化温度、合适的HOMO和LUMO能级、和较高的Eg，能够在不发生分解和没有残留物的情况下进行升华，可有效提升OLED器件的发光性能以及OLED器件的寿命，适用于磷光和荧光的OLED器件，尤其是在使用该化合物作为空穴注入材料和/或空穴传输材料时情况如此。

Description

含螺二芴结构的有机化合物及其应用 技术领域
本发明属于有机电致发光(有机EL，也称作OLED)技术领域，具体涉及一种可用于OLED器件的含螺二芴结构的有机化合物，及其在OLED器件中的应用，并且还涉及含有该有机化合物的OLED器件。
背景技术
OLED器件具备自发光、对比度高、色彩饱和度佳、视角宽、反应速度快和可卷曲等优点，是目前公认的最有前景的新一代显示技术。无机光电材料是由硬梆梆的金属、类金属、半导体元素组成的块材，整体一块，无法弯曲；有别于此，OLED材料由有机分子堆栈构成连续性薄膜，每层薄膜厚度不到0.0001公分(即次微米等级)，柔软可弯曲，能自由应用于物联网、穿戴式装置、军事飞行器等。若应用在白光照明上，OLED还具有节能的优点，所以是光电材料的当红成员。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构，产业上应用的OLED器件通常包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EML)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)等多种膜层，这意味着OLED器件的光电功能材料至少包括空穴注入材料、空穴传输材料、发光材料、电子传输材料等。光电功能材料的材料类型和搭配形式具有丰富性和多样性的特点，而对于不同结构的OLED器件而言，所使用的光电功能材料具有较强的选择性。
螺二芴分子具有非平面的空间结构，两个芴单体以sp 3杂化的C原子为中心桥联在一起。将其引入到具有电致发光特性的分子中，对于提高分子的热稳定性和光谱稳定性等具有潜在的高应用价值。
发明内容
本发明的目的在于提供一种含二芳基胺取代基团的螺二芴结构的有机化合物，该化合物具有非平面的空间结构、较高的玻璃化温度、合适的HOMO和LUMO能级、和较高的Eg，能够在不发生分解和没有残留物的情况下进行升华，可有效提升OLED器件的发光性能以及OLED器件的寿命，适用于磷光和荧光(含TADF)的OLED器 件，尤其是在使用该化合物作为空穴注入材料和/或空穴传输材料时情况如此。
具体来说，本发明的含二芳基胺取代基团的螺二芴结构的有机化合物，具有下述化学式(1)所示的结构：
Figure PCTCN2020075971-appb-000001
其中，
环A、B和C单独或同时存在，各自独立地表示经取代或未经取代的环上具有6-18个碳原子的缩合芳基或异芳基；
Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地表示经取代或未经取代的芳基或杂环芳基，并且Ar 1和Ar 2可通过E 1彼此连接成环，Ar 3和Ar 4可通过E 2彼此连接成环，Ar 5和Ar 6可通过E 3彼此连接成环；
E 1、E 2、E 3各自独立地表示直接键、O、S、CRR’或NR，其中R和R’各自独立地表示C 1-C 8的直链或支链烷基、C 1-C 8的烷氧基、C 7-C 14的芳烷基；
S 1、S 2、S 3各自独立地表示直接键、经取代或未经取代的亚芳基、经取代或未经取代的亚杂芳基；
m、n、t各自独立地表示0至3的整数；
R 1、R 2、R 3、R 4各自独立地表示氢、氘、卤素、腈基、经取代或未经取代的烷基、经取代或未经取代的环烷基、经取代或未经取代的烷氧基、经取代或未经取代的芳基、经取代或未经取代的芳氧基、经取代或未经取代的烷基芳基、经取代或未经取代的芳烷基、经取代或未经取代的芳烯基、或者经取代或未经取代的杂环基；
x和y各自独立地表示0或1，且两者不同时为0。
作为本发明的优选技术方案，环A、B和C单独存在，即仅存在A或B或C。进一步优选地，环A、B和C各自独立地表示苯环。
优选地，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地具有6-60个碳原子，且各自独立地表示经取代或未经取代的苯基、经取代或未经取代的联苯基、经取代或未经取 代的三联苯基、经取代或未经取代的四联苯基、经取代或未经取代的萘基、经取代或未经取代的菲基、经取代或未经取代的芴基、经取代或未经取代的螺二芴基、经取代或未经取代的二苯并噻吩基、经取代或未经取代的二苯并呋喃基、或者经取代或未经取代的咔唑基。
优选地，S 1、S 2、S 3各自独立地表示直接键、C 6-C 20的亚芳基或亚杂芳基。更为优选地，S 1、S 2、S 3表示直接键，即螺二芴结构和N原子直接相连。
优选地，R 1、R 2、R 3、R 4各自独立地表示氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、新戊基、环戊基、正己基、新己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟乙基、苯基、1-萘基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、2-甲基丁氧基、正戊氧基、仲戊氧基、新戊氧基、环戊氧基、正己氧基、新己氧基、环己氧基、正庚氧基、环庚氧基、正辛氧基、环辛氧基、2-乙基己氧基、三氟甲氧基、五氟乙氧基。更为优选地，R 1、R 2、R 3、R 4各自独立地表示氢或苯基。
在本发明的一个优选实施方式中，式(1)结构中的S 1、S 2和S 3均为直接键，环A、B和C以苯环结构单独存在。即，本发明的螺二芴结构的有机化合物选自如下式(2)-(4)的化合物：
Figure PCTCN2020075971-appb-000002
进一步优选地，R 1、R 2、R 3、R 4均表示氢，即，本发明的螺二芴结构的有机化合物选自如下式(2-1)-(4-1)的化合物：
Figure PCTCN2020075971-appb-000003
特别优选地，本发明的螺二芴结构的有机化合物选自式(2-1)的化合物，且x和y之和等于1。即，优选自如下式(2-2)和(2-3)的化合物：
Figure PCTCN2020075971-appb-000004
作为优选技术方案，上述各通式结构中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地，选自下列结构：
Figure PCTCN2020075971-appb-000005
其中，虚线表示与氮键合的连接位；R 5各自独立地表示甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、环庚基、正辛基、苯基、4-叔丁基苯基、环烷基。
非限制性地，以下为本发明所述化合物的部分优选示例：
Figure PCTCN2020075971-appb-000006
Figure PCTCN2020075971-appb-000007
Figure PCTCN2020075971-appb-000008
Figure PCTCN2020075971-appb-000009
在确定本发明上述有机化合物及其结构特征后，如何制备该化合物对有机化学领域的技术人员来说是容易确定的。实践表明，可采用多种路径合成目标产物。
示例性地，如下所示的合成方法是较为优选的。
方法一：
(1)式(2-2)化合物的合成
Figure PCTCN2020075971-appb-000010
由原料A在正丁基锂试剂作用下与溴代芴酮加成，得到中间体醇B，水解后环合生成二卤代苯并螺二芴C，然后与二芳基胺分步进行C-N偶联反应，先得到单二芳基胺取代的化合物D，再得到式(2-2)化合物。
(2)式(2-3)化合物的合成
Figure PCTCN2020075971-appb-000011
由原料A’在正丁基锂试剂作用下与二卤代芴酮加成，得到中间体醇B’，水解后环合生成二卤代苯并螺二芴C’，然后与二芳基胺分步进行C-N偶联反应，先得到单二芳基胺取代的化合物D’，再得到式(2-3)化合物。
方法二：
式(2-2)化合物的合成
Figure PCTCN2020075971-appb-000012
由1-溴-2-萘甲酸甲酯(E)与溴代苯硼酸反应得到中间产物F，然后水解生成中间体G，成环后得到中间体H；在正丁基锂试剂作用下，中间体H与二卤代联苯反应，得到中间体醇B”，水解后环合生成二卤代苯并螺二芴C”，然后与二芳基胺分步进行C-N偶联反应，得到式(2-2)化合物。
容易理解的是，在上述合成路线中，若最终产物中的两个二芳基胺取代基相同，则可简化中间体二卤代苯并螺二芴与二芳基胺分步进行C-N偶联反应的步骤，直接由二卤代苯并螺二芴与同一种二芳基胺进行C-N偶联反应即可得到产物。
作为本发明的另一个目的，本发明还涉及上述含二芳基胺取代基团的螺二芴结构的有机化合物在OLED器件中的应用，以及含有该有机化合物的OLED器件。
作为示例性实施方案，所述OLED器件包括：第一电极；设置成面向第一电极的第二电极；以及设置在第一电极与第二电极之间的一个或多个有机材料层，其中有机材料层中的一个或多个层包含本发明的上述有机化合物。
有机材料层可以由单层结构构成，也可以由其中堆叠有两个或更多个有机材料层的多层结构构成。例如，本发明的发光器件可以具有包括空穴注入层、空穴传输层、发光层、电子传输层、电子注入层等作为有机材料层的结构。器件结构不限于此，也可以包括较少数量的有机层。
作为另一种示例性实施方案，有机材料层包括空穴传输层，且空穴传输层包含本发明的上述有机化合物。
作为示例性实施方案，有机材料层包括空穴注入层和空穴传输层，其中空穴传输层包含本发明的上述有机化合物，空穴注入层使用具有下列结构式的化合物HAT-CN：
Figure PCTCN2020075971-appb-000013
作为示例性实施方案，有机材料层包括空穴注入层，空穴注入层包含本发明的上述有机化合物。
进一步地，除了本发明的上述有机化合物之外，空穴注入层还包含以1-20wt％的掺杂浓度掺杂的p型掺杂材料，p型掺杂材料的化学结构式如下：
Figure PCTCN2020075971-appb-000014
p型掺杂材料。
作为示例性实施方案，有机材料层包括空穴注入层和空穴传输层，且空穴注入层与空穴传输层均包含本发明的上述有机化合物。
作为示例性实施方案，有机材料层还包括电子阻挡层，电子阻挡层使用以下化学结构的化合物HT2：
Figure PCTCN2020075971-appb-000015
作为示例性实施方案，有机材料层还包括发光层，并且发光层使用化合物BH作为主发光体，化合物BD作为客发光体，其中客发光体的掺杂比例在1-10重量％，两者的化学结构式如下：
Figure PCTCN2020075971-appb-000016
作为示例性实施方案，有机材料层还包括电子传输层，电子传输层使用以下化学结构的化合物ET，并且包含掺杂50重量％的喹啉锂(Lithium 8-quinolinolate，简写成Liq)：
Figure PCTCN2020075971-appb-000017
作为示例性实施方案，有机材料层还包括电子注入层，电子注入层可使用的化合物有氟化锂(LiF)、氟化铯(CsF)、Liq、Yb等。
根据所使用的材料，本发明的OLED器件可以为顶部发光型、底部发光型或双向发光型。
将本发明的上述有机化合物用于OLED器件的有机材料层，特别是当用于空穴注入和/或空穴传输材料时，能够提高器件的效率、降低驱动电压和/或提升寿命特性，器件具有低驱动电压及长使用寿命，展现出了高稳定性的器件性能。
附图说明
图1为器件应用性能表征中OLED器件的结构示意图；其中，
1、透明基板，2、阳极层，3、空穴注入层，4、空穴传输层，5、电子阻挡层，6、发光层，7、电子传输层，8、电子注入层，9、阴极层。
具体实施方式
通过以下实施例更详细地解释本发明，但不希望因此限制本发明。在该描述的基础上，本领域普通技术人员将能够在不付出创造性劳动的情况下在所公开的整个范围内实施本发明和制备根据本发明的其它化合物，和将这些化合物用于电子器件中或使用根据本发明所述的方法。
制备实施例
参照上文记载的合成工艺，制备中间体和目标化合物。
1.中间体的合成
1.1中间体H(溴代苯并芴酮)的合成
(1)中间体H1：9-溴-7H-苯并[c]芴-7-酮
Figure PCTCN2020075971-appb-000018
将实验装置充分干燥，在氮气下向1L四口烧瓶中加入1-溴-2-萘甲酸甲酯(E，113mmo1，30g)、对溴苯硼酸(114mmo1，23g)、甲苯450mL、乙醇20mL、水200mL、碳酸钾(339mmo1，47g)、四(三苯基磷)钯(1mmo1，1.2g)，加热升温至78℃回流，搅拌反应5h，TLC跟踪原料反应进程；反应完成后，停止加热，降温至25℃，分液，有机相水洗一次后，减压蒸馏除去溶剂，经柱层析提纯，得到类白色固体产物F1 23g，收率为60％。
将实验装置充分干燥，在洁净的500mL四口烧瓶中加入F1(67.4mmo1，23g)和氢溴酸200mL、二氯甲烷50mL，加热升温至60℃回流，搅拌反应8h，HPLC跟踪原料反应进程；反应结束后，停止加热，降温至25℃，分液，水相用二氯甲烷萃取一次，合并有机相水洗一次，分液，再减压除去溶剂，经柱层析提纯，得到黄色固体产物G1 17.6g，收率为80％。
将实验装置充分干燥，在洁净的500mL四口烧瓶中加入G1(53.8mmo1，17.6g)和60％的硫酸溶液250mL，加热升温至100℃，搅拌反应12h，HPLC跟踪原料反应进程；反应结束后停止加热，降温至25℃，将反应液倒入大量冰水中，产物析出，过滤，滤饼用清水洗涤一次，过滤，得粗品；再用二氯甲烷加热溶解，经柱层析提纯， 得到黄色固体产物即H1 8.3g，收率为50％。
对产物H1的结构进行表征，结果如下所示。
1H NMR(CDCl 3,400MHz)δ:8.41～8.37(d,J＝8.0Hz,1H),7.90～7.23(m,8H)；
IR(KBr)ν:3059,3018,1760cm -1；
MS[M+H] +＝308.99。
(2)中间体H2-H4
参照中间体H1的制备方法，通过采用不同原料合成中间体H2-H4。具体如下表1中所示。
表1
Figure PCTCN2020075971-appb-000019
注：1.实施例H2和H3原料相同，根据关环位置不同，可得到两种产物，利用柱层析对两种物质进行分离。
2.表1中收率表示最后一步反应的实际收率。
1.2中间体C(二卤代苯并螺二芴)的合成
(1)中间体C1：2'-溴-9-氯螺[苯并[c]芴-7,9'-芴]
Figure PCTCN2020075971-appb-000020
将实验装置充分干燥，在氮气下向1L四口烧瓶中加入原料A1(126mmo1，40g)和干燥过的四氢呋喃(400mL)，搅拌溶解后用液氮降温至-78℃以下，缓慢滴加50.6mL2.5M(126mmol)的n-BuLi正己烷溶液；滴加结束后在-78℃下搅拌1h，然后在该温度下分批加入2-溴-9-芴酮(126mmo1，32.6g)，滴加结束后在-78℃下保温1h，然后在室温下搅拌12h。待反应结束，滴加4M盐酸溶液淬灭反应，用乙酸乙酯萃取，有机相用饱和食盐水洗涤，旋干除去溶剂，得到中间体醇B1。在不进行任何提纯的情况下，再投料到1L的干燥三口烧瓶中，加入160mL乙酸和5g 36％盐酸，升温回流3h，结束反应。冷却至室温后，过滤，用水洗涤两次，干燥，柱层析提纯，得到类白色固体产物C1 35g，总收率为58％。
对产物C1的结构进行表征，结果如下所示。
1H NMR(CDCl 3,400MHz)δ:8.70(d,J＝8.0Hz,1H),8.23(d,J＝8.0Hz,1H),7.89～7.83(m,3H),7.73～7.49(m,4H),7.34(t,J＝8.0Hz,2H),7.05(t,J＝8.0Hz,2H),6.89(s,1H),6.78～6.66(m,2H)；
IR(KBr)ν:3060,3019cm -1；
MS[M+H] +＝479.02
(2)中间体C2：2'-氯-9-溴螺[苯并[c]芴-7,9'-芴]
Figure PCTCN2020075971-appb-000021
将实验装置充分干燥，在氮气下向1L四口烧瓶中加入2-溴-4'-氯-1,1'-联苯(126mmo1，33.7g)和干燥过的四氢呋喃(400mL)，搅拌溶解后用液氮降温至-78℃以下，缓慢滴加50.6mL 2.5M(126mmol)的n-BuLi正己烷溶液；滴加结束后在-78℃下搅拌1h，然后在该温度下分批加入H1(126mmo1，39g)，滴加结束后在-78℃下保温1h，然后在室温下搅拌12h。待反应结束，滴加4M盐酸溶液淬灭反应，用乙酸乙酯萃取，有机相用饱和食盐水洗涤，旋干除去溶剂，得到中间体醇B2。在不进行任何提纯的情况下，再投料到1L的干燥三口烧瓶中，加入160mL乙酸和5g 36％盐酸，升温回流3h，结束反应。冷却至室温后，过滤，用水洗涤两次，干燥，柱层析提纯，得到类白色固体产物C2 38.7g，总收率为64％。
对产物C2的结构进行表征，结果如下所示。
1H NMR(CDCl 3,400MHz)δ:8.70(d,J＝8.0Hz,1H),8.23(d,J＝8.0Hz,1H),7.89～7.83(m,3H),7.70～7.45(m,4H),7.34(t,J＝8.0Hz,2H),7.05(t,J＝8.0Hz,2H),6.84(s,1H),6.78～6.66(m,2H)；
IR(KBr)ν:3060,3019cm -1；
MS[M+H] +＝479.03。
(3)中间体C3-C18
参照中间体C1或C2的制备方法，通过采用不同原料合成中间体C3-C18。具体如下表2中所示。
表2
Figure PCTCN2020075971-appb-000022
Figure PCTCN2020075971-appb-000023
Figure PCTCN2020075971-appb-000024
1.3中间体D(单二芳基胺取代的卤代苯并螺二芴)的合成
由中间体C和二芳基胺分步进行C-N偶联反应，即可得到最终的目标化合物。在此过程中，可利用不同的卤取代基团的反应活性差异，经由分步C-N偶联反应，先得到单二芳基胺取代的卤代苯并螺二芴，即中间体D。
(1)中间体D1
Figure PCTCN2020075971-appb-000025
将实验装置充分干燥，在氮气下向500mL四口烧瓶中加入C1即2'-溴-9-氯螺[苯并[c]芴-7,9'-芴]21.6g(45mmol)和17.9g(49.5mmol)N-[1,1'-联苯-4-基]-9,9-二甲基-9H-芴-2-胺，再加入干燥并脱气过的甲苯作溶剂，加入6.5g(67.5mmol)叔丁醇钠、1.1g(1.13mmol)催化剂Pd 2(dba) 3和1.2g(2.25mmol)1,1'-双(二苯基膦)二茂铁，升温至100-105℃，反应16h。待反应结束，冷却至室温，用甲苯稀释，垫硅胶过滤，滤液真空蒸去溶剂，得到粗品，粗品用柱层析提纯，得到19.5g产物D1，收率为57％。
MS[M+H] +＝759.25。
(2)中间体D2-D10
通过采用不同原料合成中间体D2-D10。具体如下表3中所示。
表3
Figure PCTCN2020075971-appb-000026
Figure PCTCN2020075971-appb-000027
2.目标化合物的合成
上述单二芳基胺取代的卤代苯并螺二芴与二芳基胺进一步发生C-N偶联反应，即可制得本发明的目标化合物。
(1)实施例1：合成化合物1-12
Figure PCTCN2020075971-appb-000028
将实验装置充分干燥，在氮气下向500mL四口烧瓶中加入D1(34.2g，45mmol)和N-苯基-4-联苯胺12.1g(49.5mmol)，再加入干燥并脱气过的甲苯作溶剂，加入6.5g(67.5mmol)叔丁醇钠和0.88g(0.96mmol)催化剂Pd 2(dba) 3，升温至80℃，缓慢滴加4.5 mL质量浓度为10％的三叔丁基膦甲苯溶液，滴加完毕后升温至100-105℃，反应6h。待反应结束，冷却至室温，用甲苯稀释，垫硅胶过滤，滤液真空蒸去溶剂，得到粗品，粗品用柱层析提纯，得到26.6g产物1-12，收率为61％。
对产物1-12的结构进行表征，结果如下所示。
1H NMR(CDCl 3,400MHz)δ:8.20～7.85(m,8H),7.76(d,J＝8.0Hz,4H),7.56(d,J＝8.0Hz,5H),7.50(t,J＝8.0Hz,4H),7.48～7.40(m,5H),7.38(d,J＝8.0Hz,4H),7.35～7.29(m,4H),7.27～7.19(m,6H),7.15～7.05(m,5H),6.98(t,J＝8.0Hz,1H),1.68(s,6H)；
MS[M+H] +＝968.42。
(2)实施例2：合成化合物1-98
Figure PCTCN2020075971-appb-000029
将实验装置充分干燥，在氮气下向四口烧瓶中加入C10(23.6g，45mmol)和N-苯基-4-联苯胺22.3g(91mmol)，再加入干燥并脱气过的甲苯作溶剂，加入6.5g(67.5mmol)叔丁醇钠和0.88g(0.96mmol)催化剂Pd 2(dba) 3，升温至80℃，缓慢滴加4.5mL质量浓度为10％的三叔丁基膦甲苯溶液，滴加完毕后升温至100-105℃，反应6h。待反应结束，冷却至室温，用甲苯稀释，垫硅胶过滤，滤液真空蒸去溶剂，得到粗品，粗品用柱层析提纯，得到25.7g产物1-98，收率为67％。
对产物1-98的结构进行表征，结果如下所示。
1H NMR(CDCl 3,400MHz)δ:8.77～7.75(d,J＝8.2Hz,1H),8.22～8.20(d,J＝8.0Hz,1H),8.02～8.01(d,J＝8.0Hz,1H),7.88～7.74(m,4H),7.76(d,J＝8.0Hz,4H),7.57～7.54(m,5H),7.50(t,J＝8.0Hz,4H),7.45～7.36(m,9H),7.25～7.22(m,6H),7.10～7.00(m,9H)；
MS[M+H] +＝852.36。
(3)实施例3-8
参照化合物1-12及1-98的制备方法，以不同的中间体C或D和二芳基胺为原料，合成相应的目标化合物。具体如下表4所示。
表4
Figure PCTCN2020075971-appb-000030
Figure PCTCN2020075971-appb-000031
Figure PCTCN2020075971-appb-000032
性能表征
3.化合物物理性能
以部分化合物为例，对本发明的有机化合物的热性能、HOMO能级和LUMO能级进行检测。检测对象及其结果如下表5所示。
表5
化合物 Tg Td HOMO LUMO 功能层
1-2 157 480 5.22 2.28 HIL，HTL，EBL，EML
1-36 160 488 5.29 2.26 HIL，HTL，EBL，EML
1-6 165 492 5.38 2.25 HIL，HTL，EBL，EML
1-43 172 497 5.43 2.27 HIL，HTL，EBL，EML
1-86 189 502 5.45 2.23 HIL，HTL，EBL，EML
其中，玻璃化温度Tg由示差扫描量热法(DSC，美国TA公司DSC25示差扫描量热仪)测定，升温速率10℃/min；热失重温度Td是在氮气气氛中失重5％的温度，在美国TA公司的TGA55热重分析仪上进行测定，氮气流量为20mL/min；最高占据分子轨道HOMO能级和最低未占分子轨道LUMO能级，是由循环伏安法测得。
由表5数据可知，本发明化合物有较高的玻璃化转变温度，可以保证化合物的热稳定性，从而避免化合物的非结晶性薄膜转变成结晶性薄膜，使得所制作的含有本发明有机化合物的OLED器件的寿命得到提升。同时，本发明化合物具有不同的HOMO和LOMO能级，可应用于OLED器件不同的功能层。
特别地，如表5中所示，本发明的有机化合物特别适用于OLED器件中的空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)和/或发光层(EML)。它们可作为单独的层，也可作为HIL、HTL、EBL或EML中的混合组分。
4.OLED器件应用
以下结合附图1，通过器件实施例1-10和比较实施例1-2详细说明本发明的有机化合物在OLED器件中作为不同功能层材料的应用效果。
器件实施例和比较实施例中使用到的其它材料均为现有的已知在售产品，可由市场采购获得。使用到的有机材料的结构式如下：
Figure PCTCN2020075971-appb-000033
(1)器件实施例1
参照图1所示结构，制造OLED器件，具体步骤为：将镀有厚度为130nm的ITO(氧化铟锡)的玻璃基板(康宁玻璃50mm*50mm*0.7mm)分别用异丙醇和纯水超声洗涤5分钟，再用紫外线臭氧清洗，之后将玻璃基板传送至真空沉积室中；将空穴注入材料HAT-CN以5nm的厚度真空(约10 -7Torr)热沉积在透明ITO电极上，由此形成空穴注入层；在空穴注入层上真空沉积140nm厚度的化合物1-2，形成空穴传输层；在空穴传输层上真空沉积10nm厚度的HT2，形成电子阻挡层；作为发光层，真空沉积主体BH和4％的客体掺杂剂BD，厚度为25nm；使用包含掺杂50％Liq(8-羟基喹啉锂)的ET化合物形成电子传输层，厚度为25nm；最后按顺序沉积1nm厚的氟化锂(电子注入层)和100nm厚度的铝形成阴极；将该器件从沉积室传送至手套箱中，随即用UV可固化环氧树脂及含有吸湿剂的玻璃盖板进行封装。
该器件结构表示为：ITO(130nm)/HAT-CN(5nm)/化合物1-2(140nm)/HT2(10nm)/BH:BD(25nm)/ET:Liq(25nm)/LiF(1nm)/Al(100nm)。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
在上述制造步骤中，有机材料、氟化锂和铝的沉积速率分别保持在0.1nm/s、0.05nm/s和0.2nm/s。
(2)器件实施例2
以与器件实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-36代替实施例1中的化合物1-2。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
(3)器件实施例3
以与器件实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-6代替实施例1中的化合物1-2。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
(4)器件实施例4
以与器件实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-43代替实施例1中的化合物1-2。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
(5)器件实施例5
以与器件实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用化合物1-86代替实施例1中的化合物1-2。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
(6)比较实施例1
以与器件实施例1中相同的方式进行实验，不同之处在于：作为空穴传输层，使用HT1代替实施例1中的化合物1-2。所制作的OLED发光器件器件结构如表6所示，测试结果如表7所示。
表6
Figure PCTCN2020075971-appb-000034
与比较实施例1相比，上述器件实施例1-5中器件制作工艺完全相同，并且采用了相同的基板和电极材料，电极材料的膜厚也保持一致，不同的是对器件中的空穴传 输材料HT1做了更换。各实施例所得器件的性能在10mA/cm 2电流密度下测试结果如表7所示。
表7
Figure PCTCN2020075971-appb-000035
其中，发光颜色用CIE x,y色度坐标来判别与定义；驱动电压是指亮度为1cd/m 2的电压；电流效率是指单位电流密度下的发光亮度；发光效率是指消耗单位电功率所产生的光通量；外部量子效率(external quantum efficiency,EQE)是指在观测方向上射出组件表面的光子数目与注入电子数目的比率；LT95@1000nits是指以1000nits为初始亮度，器件在恒定电流条件下亮度从初始100％降低到95％的时间。
如上表所示，器件实施例1-5中使用的化合物用作有机发光器件中的空穴传输层，与联苯胺型材料HT1相比，具有优异的空穴传输的能力而表现出低电压和高效率特性。同时，基于高三重态能量(螺环材料的特性)而表现出更好的稳定性及寿命。可见包含本发明的有机发光器件具有低驱动电压及长使用寿命，展现高稳定性的器件性能。
为进一步验证本发明的应用性能优势，参照上述实施例1的方式，制造具有如表8中所示结构的OLED器件。
表8
Figure PCTCN2020075971-appb-000036
Figure PCTCN2020075971-appb-000037
与比较实施例2相比，本发明的器件实施例6-10的器件制作工艺完全相同，并且采用了相同的基板和电极材料，电极材料的膜厚也保持一致，所不同的是对器件中的空穴注入材料和空穴传输材料做了更换，并在空穴注入层掺杂了2wt％的p型掺杂材料。
将上述器件实施例6-10和比较实施例2所得器件在10mA/cm 2电流密度下进行性能测试，结果如表9所示。
表9
Figure PCTCN2020075971-appb-000038
器件实施例6-10中使用的化合物用作有机发光器件中的空穴注入层主体材料、空穴传输层，同时在空穴注入层掺杂了p型掺杂化合物，与联苯胺型材料相比，具有优异的空穴注入、传输能力而表现出低电压和高效率特性，同时，也表现出更好的稳定性及寿命。可见包含本发明的有机发光器件具有低驱动电压及长使用寿命，展现高稳定性的器件性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (22)

  1. 一种含二芳基胺取代基团的螺二芴结构的有机化合物，具有下述化学式(1)所示的结构：
    Figure PCTCN2020075971-appb-100001
    其中，
    环A、B和C单独或同时存在，各自独立地表示经取代或未经取代的环上具有6-18个碳原子的缩合芳基或异芳基；
    Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地表示经取代或未经取代的芳基或杂环芳基，并且Ar 1和Ar 2可通过E 1彼此连接成环，Ar 3和Ar 4可通过E 2彼此连接成环，Ar 5和Ar 6可通过E 3彼此连接成环；
    E 1、E 2、E 3各自独立地表示直接键、O、S、CRR’或NR，其中R和R’各自独立地表示C 1-C 8的直链或支链烷基、C 1-C 8的烷氧基、C 7-C 14的芳烷基；
    S 1、S 2、S 3各自独立地表示直接键、经取代或未经取代的亚芳基、经取代或未经取代的亚杂芳基；
    m、n、t各自独立地表示0至3的整数；
    R 1、R 2、R 3、R 4各自独立地表示氢、氘、卤素、腈基、经取代或未经取代的烷基、经取代或未经取代的环烷基、经取代或未经取代的烷氧基、经取代或未经取代的芳基、经取代或未经取代的芳氧基、经取代或未经取代的烷基芳基、经取代或未经取代的芳烷基、经取代或未经取代的芳烯基、或者经取代或未经取代的杂环基；
    x和y各自独立地表示0或1，且两者不同时为0。
  2. 根据权利要求1所述的有机化合物，其特征在于：环A、B和C单独存在。
  3. 根据权利要求1或2所述的有机化合物，其特征在于：环A、B和C各自独立地表示苯环。
  4. 根据权利要求1所述的有机化合物，其特征在于：Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地具有6-60个碳原子，且各自独立地表示经取代或未经取代的苯基、经 取代或未经取代的联苯基、经取代或未经取代的三联苯基、经取代或未经取代的四联苯基、经取代或未经取代的萘基、经取代或未经取代的菲基、经取代或未经取代的芴基、经取代或未经取代的螺二芴基、经取代或未经取代的二苯并噻吩基、经取代或未经取代的二苯并呋喃基、或者经取代或未经取代的咔唑基。
  5. 根据权利要求1所述的有机化合物，其特征在于：S 1、S 2、S 3各自独立地表示直接键、C 6-C 20的亚芳基或亚杂芳基；更为优选地，S 1、S 2、S 3表示直接键。
  6. 根据权利要求1所述的有机化合物，其特征在于：R 1、R 2、R 3、R 4各自独立地表示氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、2-甲基丁基、正戊基、仲戊基、新戊基、环戊基、正己基、新己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟乙基、苯基、1-萘基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、2-甲基丁氧基、正戊氧基、仲戊氧基、新戊氧基、环戊氧基、正己氧基、新己氧基、环己氧基、正庚氧基、环庚氧基、正辛氧基、环辛氧基、2-乙基己氧基、三氟甲氧基、五氟乙氧基；更为优选地，R 1、R 2、R 3、R 4各自独立地表示氢或苯基。
  7. 根据权利要求1所述的有机化合物，其特征在于：S 1、S 2和S 3均为直接键，环A、B和C以苯环结构单独存在；
    即，所述有机化合物选自如下式(2)-(4)的化合物：
    Figure PCTCN2020075971-appb-100002
  8. 根据权利要求7所述的有机化合物，其特征在于：R 1、R 2、R 3、R 4均表示氢；即，所述有机化合物选自如下式(2-1)-(4-1)的化合物：
    Figure PCTCN2020075971-appb-100003
  9. 根据权利要求8所述的有机化合物，其特征在于：所述有机化合物选自式(2-1)的化合物，且x和y之和等于1；即，选自如下式(2-2)和(2-3)的化合物：
    Figure PCTCN2020075971-appb-100004
  10. 根据权利要求1-9中任一项所述的有机化合物，其特征在于：各通式结构中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6各自独立地，选自下列结构：
    Figure PCTCN2020075971-appb-100005
    其中，虚线表示与氮键合的连接位；R 5各自独立地表示甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、环庚基、正辛基、苯基、4-叔丁基苯基、环烷基。
  11. 权利要求9所述的有机化合物的制备方法，其特征在于，采用下述方法：
    方法一：
    (1)式(2-2)化合物的合成
    Figure PCTCN2020075971-appb-100006
    由原料A在正丁基锂试剂作用下与溴代芴酮加成，得到中间体醇B，水解后环合生成二卤代苯并螺二芴C，然后与二芳基胺分步进行C-N偶联反应，先得到单二芳基胺取代的化合物D，再得到式(2-2)化合物；
    (2)式(2-3)化合物的合成
    Figure PCTCN2020075971-appb-100007
    由原料A’在正丁基锂试剂作用下与二卤代芴酮加成，得到中间体醇B’，水解后环合生成二卤代苯并螺二芴C’，然后与二芳基胺分步进行C-N偶联反应，先得到单二芳基胺取代的化合物D’，再得到式(2-3)化合物；
    方法二：
    式(2-2)化合物的合成
    Figure PCTCN2020075971-appb-100008
    由1-溴-2-萘甲酸甲酯(E)与溴代苯硼酸反应得到中间产物F，然后水解生成中间体G，成环后得到中间体H；在正丁基锂试剂作用下，中间体H与二卤代联苯反应，得到中间体醇B”，水解后环合生成二卤代苯并螺二芴C”，然后与二芳基胺分步进行C-N偶联反应，得到式(2-2)化合物。
  12. 根据权利要求11所述的制备方法，其特征在于：最终产物中的两个二芳基胺取代基相同，简化中间体二卤代苯并螺二芴与二芳基胺分步进行C-N偶联反应的步骤，直接由二卤代苯并螺二芴与同一种二芳基胺进行C-N偶联反应即可得到产物。
  13. 权利要求1-10中任一项所述的有机化合物在OLED器件中的应用。
  14. OLED器件，含有权利要求1-10中任一项所述的有机化合物。
  15. 根据权利要求14所述的OLED器件，包括：第一电极；设置成面向第一电极的第二电极；以及设置在第一电极与第二电极之间的一个或多个有机材料层，其中有机材料层中的一个或多个层包含所述的有机化合物。
  16. 根据权利要求15所述的OLED器件，其特征在于：有机材料层包括空穴传输层，且空穴传输层包含所述的有机化合物。
  17. 根据权利要求15所述的OLED器件，其特征在于：有机材料层包括空穴注入层和空穴传输层，其中空穴传输层包含所述的有机化合物，空穴注入层使用具有下列结构式的化合物HAT-CN：
    Figure PCTCN2020075971-appb-100009
  18. 根据权利要求15所述的OLED器件，其特征在于：有机材料层包括空穴注入层，空穴注入层包含所述的有机化合物。
  19. 根据权利要求18所述的OLED器件，其特征在于：除了所述的有机化合物之外，空穴注入层还包含以1-20wt％的掺杂浓度掺杂的p型掺杂材料，p型掺杂材料的化学结构式如下：
    Figure PCTCN2020075971-appb-100010
  20. 根据权利要求15所述的OLED器件，其特征在于：有机材料层包括空穴注入层和空穴传输层，且空穴注入层与空穴传输层均包含所述的有机化合物。
  21. 根据权利要求15所述的OLED器件，其特征在于：有机材料层还包括电子阻挡层、发光层、电子传输层、电子注入层中的至少一种；其中，
    电子阻挡层使用以下化学结构的化合物HT2：
    Figure PCTCN2020075971-appb-100011
    发光层使用化合物BH作为主发光体，化合物BD作为客发光体，其中客发光体的掺杂比例在1-10重量％，两者的化学结构式如下：
    Figure PCTCN2020075971-appb-100012
    电子传输层使用以下化学结构的化合物ET，并且包含掺杂50重量％的喹啉锂：
    Figure PCTCN2020075971-appb-100013
    电子注入层使用的化合物选自氟化锂(LiF)、氟化铯(CsF)、Liq、Yb。
  22. 根据权利要求14-21中任一项所述的OLED器件，其特征在于：OLED器件为顶部发光型、底部发光型或双向发光型。
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