WO2022205592A1 - 一种苯并噻吩并苯并五元杂环材料及其制备方法与应用 - Google Patents

一种苯并噻吩并苯并五元杂环材料及其制备方法与应用 Download PDF

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WO2022205592A1
WO2022205592A1 PCT/CN2021/095914 CN2021095914W WO2022205592A1 WO 2022205592 A1 WO2022205592 A1 WO 2022205592A1 CN 2021095914 W CN2021095914 W CN 2021095914W WO 2022205592 A1 WO2022205592 A1 WO 2022205592A1
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benzothienobenzoquinone
membered heterocyclic
solvent
material according
reaction
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French (fr)
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孟鸿
王胧佩
张鑫康
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北京大学深圳研究生院
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Definitions

  • the invention relates to the field of organic display, in particular to a benzothieno benzo five-membered heterocyclic material and a preparation method and application thereof.
  • Electron transport materials are the key materials of OLEDs, which need to have good electron accepting ability and can effectively transfer electrons under a certain forward bias voltage (see Introduction to Organic Electroluminescent Materials and Devices, Huang Chunhui, Li Fufu, Huang Wei, 143 page) to ensure smooth electron injection, transport and carrier balance in light-emitting devices.
  • electron transport materials need to have the following properties: (1) reversible electrochemical reducibility and sufficiently high reduction potential; (2) suitable Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied molecular orbital Orbital (Lowest Occupied Molecular Orbital, referred to as LUMO); (3) high electron mobility; (4) high glass transition temperature (Tg); (5) amorphous thin film (see OLED organic electroluminescent materials and Devices, Chen Jinxin, Huang Xiaowen, 52 pages).
  • HOMO Highest Occupied Molecular Orbital
  • LUMO lowest unoccupied molecular orbital Orbital
  • Tg high glass transition temperature
  • amorphous thin film see OLED organic electroluminescent materials and Devices, Chen Jinxin, Huang Xiaowen, 52 pages).
  • the object of the present invention is to provide a benzothieno benzo five-membered heterocyclic material and its preparation method and application, aiming to improve the performance between the materials through the introduction of the benzo five-membered heterocyclic ring.
  • the accumulation of ions increases the electron migration rate, and improves the stability and working life of the device.
  • a benzothienobenzoquinone five-membered heterocyclic material wherein, has the following general structural formula:
  • aromatic rings Ar 1 and Ar 2 are independently selected from substituted or unsubstituted aryl or heteroaryl groups
  • R 1 -R 8 are independently selected from hydrogen, aromatic substituents or aliphatic substituents
  • X is selected from One of oxygen or oxygen-substituted heteroatom rings, sulfur or sulfur-substituted heteroatom rings, selenium or selenium-substituted heteroatom rings.
  • the substituted or unsubstituted aryl or heteroaryl groups include, but are not limited to, benzene, thiophene, furan, and pyridine.
  • the Ar 1 and Ar 2 are independently selected from substituted or unsubstituted phenyl, naphthyl, (9,9-dialkyl)fluorenyl, (9,9-disubstituted or unsubstituted aryl)fluorene base, 9,9-spirofluorenyl, purinyl, diphenylphosphoxy, pyridine group, imidazole group, imidazole derivative group, pyrimidinyl, pyridazinyl, imidazolylpyrimidinyl, pyrazinyl, Triazinyl, triazinebiphenyl, but not limited thereto.
  • the benzothienobenzoquinone five-membered heterocyclic material wherein, the Ar 1 and Ar 2 respectively have one of the following structures:
  • X can be selected from oxygen, sulfur, selenium, and substituted heteroatom rings.
  • a kind of preparation method of benzothieno benzo five-membered heterocyclic material comprising the following steps:
  • the bromobenzothiophene derivative has one of the following structures:
  • the benzene derivatives include one or more of o-chlorobenzaldehyde, 2-methoxythiophenol, 2-methoxyphenol, and 2-methoxyselenophenol, but Not limited to this.
  • the main function of benzene derivatives is to change one of the reaction substrates under the same reaction substrate (both 3-bromobenzothiophene), which can be beneficial to benzothienobenzoquinone hetero Ring formation, therefore, can be chosen to favor the formation of benzothienobenzoquinone five-membered heterocycle derivatives.
  • the first solvent includes one or more of N,N-dimethylformamide, N-methylpyrrolidone, o-xylene, and dimethyl sulfoxide
  • the second solvent includes carbonic acid One or more of propylene ester, ethylene carbonate, and diethyl carbonate
  • the third solvent includes a mixture of benzene, toluene, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide.
  • the fourth solvent includes, but is not limited to, one or more of benzene, toluene, 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide.
  • the first solvent can be selected from a high-boiling point solvent that is favorable for dissolving the reactants
  • the second solvent can be selected from an ionic electrolyte
  • the concentration of triphenylpalladium dichloride is 5 mol%, which can maximize the reaction yield on the basis of saving catalyst.
  • the concentration of tetrakis(triphenylphosphorus) palladium is 10 mol%, and the concentration of potassium carbonate aqueous solution is 2M.
  • the catalyst can be fully utilized to maximize the reaction yield.
  • step S01 specifically includes: dissolving the raw material bromobenzothiophene derivative in a 0.1M first solvent in which the benzene derivative is dissolved in a Schrank flask under the protection of a nitrogen atmosphere, Cool in saturated ammonium chloride solution and filter. After heating at 90° C. for 15 min, the reaction solution was distilled under reduced pressure, and the first intermediate product was obtained by separation through a chromatographic column.
  • step S02 specifically includes: dissolving the first intermediate product in a second solvent at 90° C., adding N-bromosuccinimide, heating under reflux for 24 hours, and pouring the solution into water , filtered to obtain a white precipitate, the white precipitate was dissolved in dichloromethane, washed with water for several times, and the solution was separated. After drying with anhydrous sodium sulfate, spin-dried to obtain the second intermediate product.
  • step S03 specifically includes: dissolving the second intermediate product in a third solvent, adding triphenylpalladium dichloride (5mol%), 2 equivalents of potassium acetate, and Pinacol borate, heated under reflux for 24 hours, the reaction solution was dried with anhydrous sodium sulfate, and separated by a chromatographic column to obtain a benzothienobenzoquinone heterocyclic boronate product.
  • step S04 specifically includes: dissolving the benzothienobenzoic five-membered heterocyclic boronate product and the selected brominated modification group in a fourth solvent, adding in a nitrogen atmosphere Tetrakis(triphenylphosphorus)palladium (10mol%), 2M aqueous potassium carbonate solution, appropriate amount of tetrahydrofuran solution, heated under reflux for 24 hours, the reaction solution was extracted with dichloromethane, and then dried with anhydrous sodium sulfate and separated by a chromatographic column to obtain A benzothienobenzoquinone five-membered heterocyclic ring is an electron transport material.
  • a kind of synthetic method of benzothieno benzo five-membered heterocyclic material, wherein, synthetic route includes but not limited to:
  • An organic light-emitting device comprising an electron transport layer, and the material of the electron transport layer is any one of the above-mentioned benzothienobenzoquinone heterocyclic materials.
  • the organic light-emitting device includes a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer and an anode that are stacked in sequence.
  • the benzothieno benzo five-membered heterocyclic ring material provided by the present invention can effectively improve the stacking between materials through the introduction of the benzo five-membered heterocyclic ring, and adopts a plane rigid structure, which is beneficial to The material exhibits high electron mobility and improves the stability of the device; the appropriate electron withdrawing group is used as the peripheral group to adjust the HOMO and LUMO energy levels, reducing the injection energy barrier and reducing the turn-on voltage; asymmetric modification is beneficial to increase the dipole moment , increasing the triplet energy level of the molecule, blocking excitons and reducing the quenching of effective excitons in the transport layer.
  • the benzothienobenzoquinone heterocyclic material provided by the present invention is used as the electron transport material of the organic electroluminescence device, it has the advantages of high carrier mobility, improved device luminous efficiency, good thermal stability and the like.
  • FIG. 1 is a fluorescence spectrum diagram of the benzothienobenzoquinone heterocyclic material 58 prepared in the embodiment of the present invention.
  • FIG. 2 is an ultraviolet absorption spectrum diagram of the benzothienobenzoquinone heterocyclic material 58 prepared in the embodiment of the present invention.
  • FIG. 3 is a schematic structural diagram of an organic electroluminescence device prepared based on a benzothienobenzoquinone five-membered heterocyclic material as an electron transport layer in an embodiment of the present invention.
  • the present invention provides a benzothienobenzoquinone heterocyclic material and a preparation method and application thereof.
  • a benzothienobenzoquinone heterocyclic material and a preparation method and application thereof.
  • the present invention is further described below in detail. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
  • the present embodiment provides a benzothienobenzoquinone five-membered heterocyclic material, compound 1, and its synthetic route is as follows:
  • the synthetic method of compound 1 specifically comprises the following steps:
  • This embodiment provides a benzothienobenzoquinone five-membered heterocyclic material, compound 218, whose synthetic route is as follows:
  • the synthetic method of compound 218 specifically comprises the following steps:
  • the synthetic method of intermediate 5 take 250mL double neck round bottom flask and add intermediate 4 (1.22g, 5mmol) and raw material 4 (0.93g, 7.5mmol), cuprous chloride (5mmol%), cesium carbonate (3.2g, 10 mmol), remove the oxygen in the system, dissolve in 1,4-dioxane, and heat under reflux for 22 h. After cooling to room temperature, the solution was poured into water and filtered to obtain a white precipitate. The crude product was recrystallized from ethanol to obtain Intermediate 5 (0.87 g, 65% yield).
  • intermediate 6 take a 250mL round-bottomed flask, connect a spherical condenser, dry and fill with nitrogen, add intermediate 5 (3.0g, 12mmol) respectively, DIBAL-H (2.13g, 15mmol) is dissolved in dry toluene A 20% wt solution was added to the system, and then heated at 65 °C for 5 h.
  • the solution was then cooled to 0°C, quenched by adding 2M aqueous sodium hydroxide solution, the solution was extracted with dichloromethane, washed several times with water until the pH of the solution was neutral, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin-dried to obtain Yellow oil (2.31 g, 85% yield).
  • the synthetic method of intermediate 8 get 100mL Schlenk bottle, add intermediate 7 (3.44g, 5mmol) and 50mL tert-butylbenzene respectively, liquid nitrogen freeze pump three times, cool to -42 °C, slowly add boron tribromide (0.68 mL, 7 mmol), slowly warmed to room temperature and continued to react for 2 h.
  • N,N-diisopropylethylamine (1.65 mL, 10 mmol) was slowly added under an ice-water bath, and the mixture was gradually heated to 120° C. to react for 24 h.
  • the reaction solution was cooled to room temperature and washed three times with sodium acetate solution.
  • the organic phase was collected and dried with anhydrous magnesium sulfate.
  • the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate was 10/1 (volume ratio)) to obtain an intermediate 8 (2.98 g, 71% yield).
  • the present embodiment provides a benzothienobenzoquinone five-membered heterocyclic material, compound 3, and its synthetic route is as follows:
  • the synthetic method of compound 3 specifically comprises the following steps:
  • the present embodiment provides a benzothienobenzoquinone five-membered heterocyclic material, compound 58, whose synthetic route is as follows:
  • the performance test of the benzothienobenzo five-membered heterocyclic material 58 prepared in Example 4 is carried out, and the results are shown in Figures 1 and 2: from the fluorescence It can be seen from the spectrogram that it has broad spectral characteristics, weak luminescence properties, and less electron loss during the transfer process; from the ultraviolet absorption spectrum of the benzothienobenzoquinone heterocyclic material 58 in Figure 2, it can be seen that, The peak position is 410 nm, and the experimentally measured energy level is 3.03 eV, which has a relatively general energy level, which can match the blue light organic light-emitting diode device, and has certain hole and exciton blocking ability.
  • the present invention provides an organic light-emitting device based on a benzothienobenzoquinone heterocyclic material as an electron transport layer, as shown in FIG. 3 , including a metal cathode 10, an electron injection layer 20, an electron The transport layer 30 , the light-emitting layer 40 , the hole transport layer 50 , the hole injection layer 60 , the anode 70 , and the glass substrate 80 .
  • the material of the metal cathode 10 is selected from aluminum;
  • the material of the electron injection layer 20 is lithium fluoride
  • the material of the electron transport layer 30 is compound 58;
  • the material of the light-emitting layer 40 is formed by co-doping the host material and the guest material, wherein the host material is selected from the compound 2,6-DCzppy with the following structure, the guest material is selected from the Firpic with the following structure, and the mass ratio of the host material to the guest material doping for 80:20:
  • the material of the hole transport layer 50 is selected from the compound NPB with the following structure:
  • the material of the hole injection layer 60 is selected from the compound HATCN with the following structure:
  • the material of the anode 70 is indium tin oxide.
  • Example 5 The device prepared in Example 5 was tested for performance, and the results are shown in Table 1:
  • benzothienobenzoquinone five-membered heterocyclic ring material 58 provided in the embodiment of the present invention can match most light-emitting layers, and has certain hole and exciton blocking capabilities.
  • the present invention provides a benzothieno benzo five-membered heterocyclic material, which can effectively improve the stacking between materials through the introduction of the benzo five-membered heterocyclic ring, and adopts a plane rigid structure, It is beneficial for the material to exhibit high electron mobility and improve the stability of the device; the appropriate electron withdrawing group is used as the peripheral group to adjust the HOMO and LUMO energy levels, reducing the injection energy barrier and reducing the turn-on voltage; asymmetric modification is beneficial to the dipole. The moment increases, elevates the triplet energy level of the molecule, blocks excitons and reduces the quenching of effective excitons in the transport layer.
  • the benzothienobenzoquinone heterocyclic material provided by the present invention is used as the electron transport material of the organic electroluminescence device, it has the advantages of high carrier mobility, improved device luminous efficiency, good thermal stability and the like.

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Abstract

公开了一种苯并噻吩并苯并五元杂环材料及其制备方法与应用，所述材料具有以下结构通式(I)：其中，芳香环Ar 1和Ar 2分别独立地选自取代或未取代的芳基或杂芳基，R 1-R 8分别独立地选自氢、芳香族取代基或脂肪族取代基，X选自氧、硫、硒以及取代的上述杂原子环。通过苯并五元杂环的引入，可有效改善材料之间的堆积，化合物采用平面刚性结构，有利于表现出高电子迁移率以及提高稳定性。采用恰当的吸电子基作为外围基团调节HOMO、LUMO能级，减小注入能垒，降低启亮电压；不对称修饰利于偶极矩增加，提高分子三线态能级，阻挡激子并减少有效激子在传输层的淬灭，其作为有机电致发光器件的电子传输材料时，具有载流子迁移率高、器件性能优异和稳定性好等优点。

Description

一种苯并噻吩并苯并五元杂环材料及其制备方法与应用 技术领域
本发明涉及有机显示领域，尤其涉及一种苯并噻吩并苯并五元杂环材料及其制备方法与应用。
背景技术
有机材料的电致发光现象最早可以追溯到1963年，Pope等人发现单层蒽(anthracene)晶体作为电子传输层发出微弱的蓝光，但因为驱动电压高达100V以上未得到发展。直到1987年，美国Kodak公司的C.W.Tang等人使用8-羟基喹啉铝(AlQ3)作为电子传输层制备的有机发光二极管(Organic Light Emission Diodes，OLED)，启亮电压低至几伏特，亮度高达1000cd/m 2，有机发光器件才取得了极大的进步。
电子传输材料是OLED的关键材料，其需要有良好的电子接受能力，可在一定的正向偏压下有效传递电子(参见有机电致发光材料与器件导论，黄春辉、李富有、黄维，143页)，以保证在发光器件中电子的顺利注入、传输以及载流子的平衡。这就使得电子传输材料需要具备以下性质：(1)可逆的电化学还原性和足够高的还原电位；(2)合适的最高占据分子轨道(Highest Occupied Molecular Orbital，简称HOMO)和最低未占分子轨道(Lowest Occupied Molecular Orbital，简称LUMO)；(3)较高的电子迁移率；(4)高的玻璃化转变温度(Tg)；(5)非结晶性薄膜(参见OLED有机电致发光材料与器件，陈金鑫、黄孝文著，52页)。
然而，目前的电子传输材料在性能上还有待于进一步的改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种苯并噻吩并苯并五元杂环材料及其制备方法与应用，旨在通过苯并五元杂环的引入，改善材料之间的堆积，提升电子迁移速率，提高器件稳定性和工作寿命。
本发明的技术方案如下：
一种苯并噻吩并苯并五元杂环材料，其中，具有以下结构通式：
Figure PCTCN2021095914-appb-000001
其中，芳香环Ar 1和Ar 2分别独立地选自取代或者未取代的芳基或杂芳基，R 1-R 8分别独立地选自氢、芳香族取代基或者脂肪族取代基，X选自氧或者氧取代的杂原子环、硫或者硫取代的杂原子环、硒或者硒取代的杂原子环中的其中一种。
所述取代或者未取代的芳基或杂芳基包括但不限于苯、噻吩、呋喃、吡啶。
所述Ar 1和Ar 2分别独立地选自取代或者未取代的苯基、萘基、(9，9-二烷基)芴基、(9，9-二取代或者未取代的芳基)芴基、9，9-螺芴基、嘌呤基、二苯基磷氧基、吡啶基团、咪唑基团、咪唑衍生物基团、嘧啶基、哒嗪基、咪唑联嘧啶基、吡嗪基、三嗪基、三嗪联苯基，但不限于此。
所述的苯并噻吩并苯并五元杂环材料，其中，所述Ar 1和Ar 2分别具有以下结构的一种：
Figure PCTCN2021095914-appb-000002
其中，
Figure PCTCN2021095914-appb-000003
表示连接位点。
所述的苯并噻吩并苯并五元杂环材料，其中，X可选自氧、硫、硒，以及取代的上述杂原子环。
所述的苯并噻吩并苯并五元杂环材料，其中，具有以下结构中的一种：
Figure PCTCN2021095914-appb-000004
Figure PCTCN2021095914-appb-000005
Figure PCTCN2021095914-appb-000006
Figure PCTCN2021095914-appb-000007
Figure PCTCN2021095914-appb-000008
Figure PCTCN2021095914-appb-000009
Figure PCTCN2021095914-appb-000010
Figure PCTCN2021095914-appb-000011
Figure PCTCN2021095914-appb-000012
Figure PCTCN2021095914-appb-000013
Figure PCTCN2021095914-appb-000014
Figure PCTCN2021095914-appb-000015
Figure PCTCN2021095914-appb-000016
Figure PCTCN2021095914-appb-000017
Figure PCTCN2021095914-appb-000018
Figure PCTCN2021095914-appb-000019
一种苯并噻吩并苯并五元杂环材料的制备方法，其中，包括以下步骤：
S01、提供溴代苯并噻吩衍生物原料，加入到溶有苯衍生物的第一溶剂中，在饱和氯化铵溶液中冷却、过滤，反应后得到第一中间产物；
S02、将所述第一中间产物溶于第二溶剂中，加入N-溴代琥珀酰亚胺，反应后过滤得到白色沉淀，将所述白色沉淀溶解于二氯甲烷中，反应后得到第二中间产物；
S03、将所述第二中间产物溶于第三溶剂中，在氮气气氛中加入三苯基二氯化钯、2当量的醋酸钾、联硼酸频哪醇酯，反应后得到苯并噻吩并苯并五元杂环硼酸酯产物；
S04、将所述苯并噻吩并苯并五元杂环硼酸酯产物与溴代修饰基团溶解于第四溶剂中，在氮气气氛中加入四(三苯基磷)钯、碳酸钾水溶液、四氢呋喃溶液，反应后得到以苯并噻吩并苯并五元杂环为核的材料。
在一些实施方式中，所述溴代苯并噻吩衍生物具有以下结构中的一种：
Figure PCTCN2021095914-appb-000020
在一些实施方式中，所述苯衍生物包括邻氯苯甲醛、2-甲氧基苯硫酚、2-甲氧基苯酚、2-甲氧基苯硒酚中的一种或多种，但不限于此。
在该步骤中，苯衍生物的主要作用是在反应底物相同的情况下(同为3-溴苯并噻吩)，改变其中一种反应底物即可利于苯并噻吩并苯并五元杂环的形成，因此，可选择有利于苯并噻吩并苯并五元杂环的形成的衍生物。
在一些实施方式中，所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜的一种或多种，所述第二溶剂包括碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯的一种或多种，所述第三溶剂包括苯、甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺的一种或多种，所述第四溶剂包括苯、甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺的一种或多种，但不限于此。
其中，所述第一溶剂可选择利于反应物溶解高沸点溶剂，所述第二溶剂可选择离子型电解质。
在一些优选的实施方式中，三苯基二氯化钯浓度为5mol％，在节省催化剂的基础上，可使反应产率最大程度地得到提高。
在一些优选的实施方式中，四(三苯基磷)钯浓度为10mol％，碳酸钾水溶液浓度为2M，在节省催化剂的基础上，可充分发挥催化剂作用达到反应产率最大化。
在一些优选的实施方式中，步骤S01具体包括：在氮气气氛保护下将原料溴代苯并噻吩衍生物在施兰克瓶中溶解于0.1M的溶有苯衍生物的第一溶剂中，在饱和氯化铵溶液中冷却、过滤。90℃下加热15min后，将反应溶液减压蒸馏，通过色谱柱分离得到第一中间产物。
在一些优选的实施方式中，步骤S02具体包括：将所述第一中间产物在90℃溶解于第二溶剂中，加入N-溴代琥珀酰亚胺，加热回流24小时，将溶液倒入水中，过滤得到白色沉淀，将白色沉淀溶解于二氯甲烷，中加水洗涤若干次，分液。用无水硫酸钠干燥后旋干得到第二中间产物。
在一些优选的实施方式中，步骤S03具体包括：将所述第二中间产物溶于第三溶剂中，在氮气气氛中加入三苯基二氯化钯(5mol％)、2当量醋酸钾、联硼酸频哪醇酯，加热回流24小时，将反应溶液用无水硫酸钠干燥，通过色谱柱分离得到苯并噻吩并苯并五元杂环硼酸酯产物。
在一些优选的实施方式中，步骤S04具体包括：将所述苯并噻吩并苯并五元杂环硼酸酯产物与所选溴代修饰基团溶解于第四溶剂中，在氮气气氛中加入四(三苯基磷)钯(10mol％)、2M碳酸钾水溶液、适量四氢呋喃溶液，加热回流24小时，将反应溶液用二氯甲烷萃取分液，用无水硫酸钠干燥后通过色谱柱分离得到苯并噻吩并苯并五元杂环为核的电子传输材料。
一种苯并噻吩并苯并五元杂环材料的合成方法，其中，合成路线包括但不限于：
Figure PCTCN2021095914-appb-000021
或者
Figure PCTCN2021095914-appb-000022
一种有机发光器件，其中，包括电子传输层，所述电子传输层材料为如上任一所述的苯并噻吩并苯并五元杂环材料。
所述的有机发光器件，其中，包括依次层叠设置的金属阴极、电子注入层，电子传输层、发光层、空穴传输层、空穴注入层以及阳极。
有益效果：本发明提供的一种苯并噻吩并苯并五元杂环材料，通过苯并五元杂环的引入，可以有效的改善材料之间的堆积，并且采用了平面刚性结构，有利于材料表现出高电子迁移率，提高器件的稳定性；采用恰当的吸电子基作为外围基团调节HOMO、LUMO能级，减小注入能垒，降低启亮电压；不对称修饰利于偶极矩增加，提高分子三线态能级，阻挡激子并减少有效激子在传输层的淬灭。采用本发明提供的苯并噻吩并苯并五元杂环材料作为有机电致发光器件的电子传输材料时，具有载流子迁移率高、器件发光效率得到提升以及热稳定性好等优点。
附图说明
图1为本发明实施例中所制备的苯并噻吩并苯并五元杂环材料58的荧光光谱图。
图2为本发明实施例中所制备的苯并噻吩并苯并五元杂环材料58的紫外吸收光谱图。
图3为本发明实施例中基于苯并噻吩并苯并五元杂环材料作为电子传输层所制备的有机电致发光器件较佳的结构示意图。
具体实施方式
本发明提供一种苯并噻吩并苯并五元杂环材料及其制备方法与应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
需要说明的是，本申请的说明书和权利要求书及上述附图中的术语“包括”，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设 备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。还需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可通过市购获得的常规产品。实施例中未提及合成方法的化合物均为通过商业途径获得的原料产品。
下面通过具体实施例对本发明一种苯并噻吩并苯并五元杂环材料及其制备方法与应用做进一步的解释说明：
实施例1
本实施例提供一种苯并噻吩并苯并五元杂环材料，化合物1，其合成路线如下所示：
Figure PCTCN2021095914-appb-000023
化合物1的合成方法具体包括以下步骤：
中间体1的合成：将114g硫氢化钠加入到溶有100g邻氯苯甲醛的200mLNMP溶液中，搅拌1h，然后在180℃加热搅拌10h。冷却至室温，将反应混合液倒入1L的饱和氯化铵溶液中，冰浴下冷却，将沉淀物过滤，之后用水和丙酮洗涤，再用石油醚为洗脱剂、以硅胶柱层析纯化得到中间体1(102g，产率72％)。
中间体2的合成：取500mL双颈圆底烧瓶，上接球形冷凝管，分别加入中间体1(2.38g，7.5mmol)、碳酸丙烯酯(PC)(70mL)，加热至完全溶解。冷却至室温，加入N-溴代琥珀酰亚胺(1.60g)，在90℃下反应18h。冷却至室温，将溶液倒入水中，过滤得到白色沉淀，粗产物使用乙醇重结晶得到中间体2(3.57g，产率83％)。
中间体3的合成：取100mL双颈圆底烧瓶，上接球形冷凝管，分别加入中间体2(1g，2.51mmol)，联硼酸频哪醇脂(2.54g,10mmol)，双三苯基磷二氯化钯(100mg)，过量醋酸钾(2.5g)和50mL甲苯；将反应在氮气气氛下进行多次除氧操作密封，并将反应物混合在85℃下避光搅拌24h；之后旋干甲苯，用少量二氯甲烷溶解，经水洗两遍，将水相用二氯甲烷反萃一遍，并重复此操作两遍。然后用无水硫酸镁干燥，过滤旋干；并将其用混合溶剂(石油醚/乙酸乙酯,v/v＝5:1)作为洗脱液进行柱色谱纯化，得到中间体3的白色固体，再用甲醇/二氯甲烷重结晶得无色透明晶体(0.6g，产率60％)。
化合物1的合成：取50mL圆底烧瓶，上接球形冷凝管，干燥后充入氮气，分别加入中间体3(1.83g，5mmol)，原料2(1.49g，4.16mmol)，四三苯基膦钯(115.6mg，0.1mmol)，2M碳酸钾水溶液10mL，50mL甲苯，加热回流24h。冷却至室温，将溶液倒入水中，过滤得到白色沉淀，粗产物使用柱层析色谱法分离得到化合物1(1.52g，产率67％)。
实施例2
本实施例提供一种苯并噻吩并苯并五元杂环材料，化合物218，其合成路线如下所示：
Figure PCTCN2021095914-appb-000024
化合物218的合成方法具体包括以下步骤：
中间体4的合成：在氮气气氛中，-20℃下，取Schlenk瓶将原料3溶解于(2.12g,10mmol)干燥的二氯甲烷中，加入8当量的BF 3OEt 2(12.7g，0.08mol)。再将1.2当量的mCPBA(20.7084g，0.12mol)在1.5h内分三次加入。通过TLC监测反应进程，直到反应物点完全消失。加入饱和碳酸钠水溶液和碳酸钾。用负载硫酸镁和碳酸钾的布氏漏斗过滤，之后用二氯甲烷洗涤旋干得到粗产物，再用硅胶柱层析纯化(EtOAc/CH 2Cl 2)得到中间体4(1.94g，产率80％)。
中间体5的合成方法：取250mL双颈圆底烧瓶加入中间体4(1.22g，5mmol)和原料4(0.93g，7.5mmol)，氯化亚铜(5mmol％)，碳酸铯(3.2g，10mmol)，除去体系中的氧气，溶于1,4-二氧六环中，加热回流22h。冷却至室温，将溶液倒入水中，过滤得到白色沉淀，粗产物使用乙醇重结晶得到中间体5(0.87g，产率65％)。
中间体6的合成方法：取250mL圆底烧瓶，上接球形冷凝管，干燥后充入氮气，分别加入中间体5(3.0g，12mmol)，DIBAL-H(2.13g，15mmol)溶解于干燥甲苯配成20％wt溶液加入体系，然后在65℃下加热5h。再将溶液冷却至0℃，加入2M的氢氧化钠水溶液淬灭，溶液用二氯甲烷萃取，再用水洗若干次直到溶液pH为中性，用无水硫酸镁干燥，过滤，滤液旋干得到黄色油状物(2.31g，产率85％)。
中间体7的合成：在0.9mL特戊酸中加入中间体6(0.048g，0.18mmol)以及Pd(OPiv) 2(0.006g，0.02mmol)，120℃加热20h。降温后，反应混合物用纯石油醚做洗脱剂通过硅胶柱层析得到无色固体，即得到中间体7(0.042g，0.164mmol，产率93％)。
中间体8的合成方法：取100mL Schlenk瓶，分别加入中间体7(3.44g，5mmol)和50mL叔丁基苯，液氮冻抽三次，冷却至-42℃，缓慢加入三溴化硼(0.68mL，7mmol)，缓慢升至室温继续反应2h。冰水浴下缓慢加入N,N-二异丙基乙胺(1.65mL，10mmol)， 逐渐加热至120℃反应24h。反应液冷却至室温，使用乙酸钠溶液洗涤三次，收集有机相并用无水硫酸镁干燥，粗产物以硅胶柱层析(石油醚/乙酸乙酯为10/1(体积比))纯化得到中间体8(2.98g，产率71％)。
中间体9的合成：在-15℃下，将中间体8(0.24g，1mmol)溶解于二氯甲烷中，加入吡啶(3mmol)，并缓慢滴加三氟甲磺酸酐(2mmol)二氯甲烷溶液。反应1h后用水淬灭并分液，之后用无水硫酸镁干并旋干，再用硅胶柱层析纯化(乙酸乙酯/石油醚，v/v＝1:9)得到中间体9(0.33g，产率93％)。
中间体10的合成：同中间体3的合成，区别在于使用中间体9(3.58g，5mmol)，最后得到中间体10(2.76g，产率67％)。
化合物218的合成：同化合物1的合成，区别在于使用中间体10(1.75g，5mmol)，最后得到化合物218(0.64g，产率57％)。
实施例3
本实施例提供一种苯并噻吩并苯并五元杂环材料，化合物3，其合成路线如下所示：
Figure PCTCN2021095914-appb-000025
化合物3的合成方法具体包括以下步骤：
中间体11的合成：在除过空气的80mLN,N-二甲基乙酰胺中加入原料5(2.1g，40mmol)、乙酸钠(6.7g，80mmol)和PdCl 2(PPh 3) 3(1.4g，2mmol)。加热回流24h后用200mL的1M盐酸水溶液淬灭。用乙酸乙酯萃取，之后用氯化钠水溶液洗涤，然后用无水硫酸镁干燥，旋干得到产物。再用石油醚作为洗脱液，经硅胶柱层析纯化得到纯品中间体11(1.90g，产率74％)。
中间体12的合成：同中间体2的合成，区别在于使用中间体11(5.65g，22mmol)，最后得到中间体12(5.62g，产率80％)。
中间体13的合成：同中间体3的合成，区别在于使用中间体12(3.51g，5mmol)，最后得到中间体13(2.33g，产率65％)。
化合物3的合成：同化合物1的合成，区别在于使用中间体13(2.07g，5mmol)和原料2(1.49g，4.16mmol)，最后得到化合物3(1.76g，产率75％)。
实施例4
本实施例提供一种苯并噻吩并苯并五元杂环材料，化合物58，其合成路线如下所示：
Figure PCTCN2021095914-appb-000026
化合物58的合成：同化合物1的合成，区别在于使用原料6(1.74g，6mmol)，最后得到化合物58(1.52g，产率60％)。
对实施例4制备的苯并噻吩并苯并五元杂环材料58进行性能测试，结果如图1、图2所示：由图1中苯并噻吩并苯并五元杂环材料58的荧光光谱图可知，其具有较宽的光谱特征，本身发光属性较弱，传递过程中的电子损耗较少；由图2中苯并噻吩并苯并五元杂环材料58的紫外吸收光谱图可知，其起峰位置为410nm，实验测得能级为3.03eV，具有较为普适的能级，可匹配蓝光有机发光二极管器件，且具有一定的空穴、激子阻挡能力。
实施例5
本发明提供了基于苯并噻吩并苯并五元杂环材料作为电子传输层的有机发光器件，如图3所示，包括从上至下依次层叠设置的金属阴极10、电子注入层20、电子传输层30、发光层40、空穴传输层50、空穴注入层60、阳极70以及玻璃基板80。
在本实施例中，金属阴极10的材料选用铝；
电子注入层20的材料选用氟化锂；
电子传输层30的材料选用化合物58；
发光层40的材料由主体材料和客体材料共掺杂形成，其中主体材料选用具有以下结构的化合物2,6-DCzppy，客体材料选用具有以下结构的Firpic，主体材料与客体材料掺杂的质量比为80:20：
Figure PCTCN2021095914-appb-000027
空穴传输层50的材料选用具有如下结构的化合物NPB：
Figure PCTCN2021095914-appb-000028
空穴注入层60的材料选用具有如下结构的化合物HATCN：
Figure PCTCN2021095914-appb-000029
阳极70的材料选用氧化铟锡。
对实施例5制备的器件进行性能测试，结果如表1所示：
表1：
Figure PCTCN2021095914-appb-000030
由表1可知，本发明实施例提供的苯并噻吩并苯并五元杂环材料58可以匹配多数发光层，并且具有一定的空穴、激子阻挡能力。
综上所述，本发明提供了一种苯并噻吩并苯并五元杂环材料，通过苯并五元杂环的引入，可以有效的改善材料之间的堆积，并且采用了平面刚性结构，有利于材料表现出高电子迁移率，提高器件的稳定性；采用恰当的吸电子基作为外围基团调节HOMO、LUMO能级，减小注入能垒，降低启亮电压；不对称修饰利于偶极矩增加，提高分子三线态能级，阻挡激子并减少有效激子在传输层的淬灭。采用本发明提供的苯并噻吩并苯并五元杂环材料作为有机电致发光器件的电子传输材料时，具有载流子迁移率高、器件发光效率得到提升以及热稳定性好等优点。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

  1. 一种苯并噻吩并苯并五元杂环材料，其特征在于，具有以下结构通式：
    Figure PCTCN2021095914-appb-100001
    其中，芳香环Ar 1和Ar 2分别独立地选自取代或者未取代的芳基或杂芳基，R 1-R 8分别独立地选自氢、芳香族取代基或者脂肪族取代基，X选自氧或者氧取代的杂原子环、硫或者硫取代的杂原子环、硒或者硒取代的杂原子环中的其中一种。
  2. 根据权利要求1所述的苯并噻吩并苯并五元杂环材料，其特征在于，所述Ar 1和Ar 2分别独立地选自取代或者未取代的苯基、萘基、(9，9-二烷基)芴基、(9，9-二取代或者未取代的芳基)芴基、9，9-螺芴基、嘌呤基、二苯基磷氧基、吡啶基团、咪唑基团、咪唑衍生物基团、嘧啶基、哒嗪基、咪唑联嘧啶基、吡嗪基、三嗪基、三嗪联苯基。
  3. 根据权利要求2所述的苯并噻吩并苯并五元杂环材料，其特征在于，所述Ar 1和Ar 2分别具有以下结构的一种：
    Figure PCTCN2021095914-appb-100002
    Figure PCTCN2021095914-appb-100003
    Figure PCTCN2021095914-appb-100004
    其中，
    Figure PCTCN2021095914-appb-100005
    表示连接位点。
  4. 根据权利要求1所述的苯并噻吩并苯并五元杂环材料，其特征在于，具有以下结构中的一种：
    Figure PCTCN2021095914-appb-100006
    Figure PCTCN2021095914-appb-100007
    Figure PCTCN2021095914-appb-100008
    Figure PCTCN2021095914-appb-100009
    Figure PCTCN2021095914-appb-100010
    Figure PCTCN2021095914-appb-100011
    Figure PCTCN2021095914-appb-100012
    Figure PCTCN2021095914-appb-100013
    Figure PCTCN2021095914-appb-100014
    Figure PCTCN2021095914-appb-100015
    Figure PCTCN2021095914-appb-100016
    Figure PCTCN2021095914-appb-100017
    Figure PCTCN2021095914-appb-100018
    Figure PCTCN2021095914-appb-100019
    Figure PCTCN2021095914-appb-100020
    Figure PCTCN2021095914-appb-100021
    Figure PCTCN2021095914-appb-100022
  5. 一种苯并噻吩并苯并五元杂环材料的制备方法，其特征在于，包括以下步骤：
    提供溴代苯并噻吩衍生物原料，加入到溶有苯衍生物的第一溶剂中，在饱和氯化铵溶液中冷却、过滤，反应后得到第一中间产物；
    将所述第一中间产物溶于第二溶剂中，加入N-溴代琥珀酰亚胺，反应后过滤得到白色沉淀，将所述白色沉淀溶解于二氯甲烷中，反应后得到第二中间产物；
    将所述第二中间产物溶于第三溶剂中，在氮气气氛中加入三苯基二氯化钯、2当量的醋酸钾、联硼酸频哪醇酯，反应后得到苯并噻吩并苯并五元杂环硼酸酯产物；
    将所述苯并噻吩并苯并五元杂环硼酸酯产物与溴代修饰基团溶解于第四溶剂中，在氮气气氛中加入四(三苯基磷)钯、碳酸钾水溶液、四氢呋喃溶液，反应后得到以苯并噻吩并苯并五元杂环为核的材料。
  6. 根据权利要求5所述的苯并噻吩并苯并五元杂环材料的制备方法，其特征在于，所述溴代苯并噻吩衍生物具有以下结构中的一种：
    Figure PCTCN2021095914-appb-100023
  7. 根据权利要求5所述的苯并噻吩并苯并五元杂环材料的制备方法，其特征在于，所述苯衍生物包括邻氯苯甲醛、2-甲氧基苯硫酚、2-甲氧基苯酚、2-甲氧基苯硒酚中的一种或多种。
  8. 根据权利要求5所述的苯并噻吩并苯并五元杂环材料的制备方法，其特征在于，所述第一溶剂包括N,N-二甲基甲酰胺、N-甲基吡咯烷酮、邻二甲苯、二甲亚砜的一种或多种，所述第二溶剂包括碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯的一种或多种，所述第三溶剂包括苯、甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺的一种或多种，所述第四溶剂包括苯、甲苯、1,4-二氧六环、四氢呋喃、N,N-二甲基甲酰胺的一种或多种。
  9. 一种有机发光器件，其特征在于，包括电子传输层，所述电子传输层材料为权利要求1-4任一所述的苯并噻吩并苯并五元杂环材料。
  10. 根据权利要求9所述的有机发光器件，其特征在于，包括依次层叠设置的金属阴极、电子注入层，电子传输层、发光层、空穴传输层、空穴注入层以及阳极。
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