WO2021103769A1 - 一种化合物和含该化合物的有机电致发光器件 - Google Patents

一种化合物和含该化合物的有机电致发光器件 Download PDF

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WO2021103769A1
WO2021103769A1 PCT/CN2020/116334 CN2020116334W WO2021103769A1 WO 2021103769 A1 WO2021103769 A1 WO 2021103769A1 CN 2020116334 W CN2020116334 W CN 2020116334W WO 2021103769 A1 WO2021103769 A1 WO 2021103769A1
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substituted
unsubstituted
group
compound
aryl
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PCT/CN2020/116334
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French (fr)
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鄢亮亮
陈少福
戴雷
蔡丽菲
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广东阿格蕾雅光电材料有限公司
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Priority to JP2022529682A priority Critical patent/JP7385752B2/ja
Priority to US17/777,026 priority patent/US20230015881A1/en
Priority to DE112020004794.6T priority patent/DE112020004794T5/de
Priority to KR1020227013149A priority patent/KR20220066341A/ko
Publication of WO2021103769A1 publication Critical patent/WO2021103769A1/zh

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Definitions

  • the invention relates to the technical field of organic electroluminescence, in particular to a dibenzoheterocyclic organic compound of imidazo[1,2-a]pyridine and its application in organic electroluminescence devices.
  • OLED organic electroluminescent devices
  • the basic structure of an OLED device is a thin film of organic functional materials with various functions sandwiched between metal electrodes, which is like a sandwich structure. Under the drive of current, holes and electrons are injected from the anode and the anode, and holes and electrons are injected separately from the anode and cathode. After moving for a certain distance, the light-emitting layer is recombined and released in the form of light or heat, resulting in the luminescence of the OLED.
  • organic functional materials are the core components of organic electroluminescent devices, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. of the material are all affected The main factor of device performance.
  • organic functional materials include fluorescent materials and phosphorescent materials.
  • Fluorescent materials are usually organic small molecule materials, and generally only use 25% singlet to emit light, so the luminous efficiency is relatively low.
  • the spin-orbit coupling effect of the phosphorescent material due to the heavy atom effect can not only use 25% singlet state, but also use 75% triplet exciton energy, so the luminous efficiency can be improved.
  • the host material is generally used to match with it, in order to maximize the use of the performance of the phosphorescent materials. This puts a higher demand on the host material and the organic thin film layer adjacent to the light-emitting layer, such as hole blocking and electron blocking layer materials.
  • US9780313 discloses that a compound linked to imidazo[1,2-a]pyridine and carbazole is used as a single host in an OLED device, but the efficiency and lifetime of the device are not ideal, and further improvement is needed.
  • the inventor provides a dibenzoheterocyclic organic compound containing imidazo[1,2-a]pyridine and its application in organic electroluminescence devices.
  • the compound of the present invention has a higher glass transition temperature and higher optical, electrical and thermal stability. When used in an OLED device, it can provide improved luminous efficiency and lifetime of the device and a lower start-up voltage, and has application in OLED Industrial possibilities.
  • X is selected from the group consisting of O, S, Se, CR 3 R 4 , SiR 5 R 6 , GeR 7 R 8 , BR 9 ;
  • R 1 , R 2 , R 11 , and R 12 are unsubstituted to the maximum possible number of substitutions, and when representing multiple substitutions, two adjacent substitutions can be connected to each other to form a fused ring structure with formula (1);
  • each occurrence of R 1 -R 9 is independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2 -C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C6-C30 aralkyl, substituted or Unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl, and R 2 is not hydrogen;
  • each occurrence of R 11- R 12 is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, amino, substituted or unsubstituted C3-C30 silyl group, substituted or Unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl, cyano, nitrile, isonitrile, phosphino;
  • R 3 and R 4 , R 5 and R 6 , R 7 and R 8 can be directly bonded or bonded through O, Si, NR 3 to form a combined ring;
  • each occurrence of L is independently selected from directly linked to formula (1), substituted or unsubstituted C1-C10 alkylene, substituted or unsubstituted C1-C10 heteroalkylene, substituted or unsubstituted C6-C30 aralkylene, substituted or unsubstituted C1-C10 alkyleneoxy, substituted or unsubstituted C6-C30 aryleneoxy, imino, substituted or unsubstituted C3-C30 Silyl group, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted C2-C30 heteroarylene group or phosphinylene group;
  • substitution is substituted by deuterium, halogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C6-C18 aryl, C1-C18 heteroaryl, C1-C4 alkyl Amino or C6-C18 aryl substituted amine group substitution.
  • the compound is selected from any one of the following formulas 2 to 9;
  • R 1 is hydrogen
  • R 2 is monosubstituted or adjacent disubstituted, one of which is substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 heteroaryl, wherein Disubstituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1- The heteroaryl groups of C10 are bonded to form a ring;
  • R 11 is hydrogen or is monosubstituted or disubstituted, one of which is substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C1-C20 heteroaryl, and the disubstituted is substituted or One of unsubstituted C1-C8 alkyl, substituted or unsubstituted C2-C8 alkenyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C1-C10 heteroaryl Indirect bonding to form a ring;
  • R 12 is a C6-C10 aryl group or a C1-C10 heteroaryl group.
  • the heteroaryl group is an N heteroaryl group, wherein X is selected from the group consisting of O, S, CR 3 R 4 , BR 9 , wherein R 3 , R 4 , and R 9 are independently represented by hydrogen, Substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C6-C10 Aralkyl, substituted or unsubstituted C6-C10 aryl.
  • X is selected from the group consisting of O, S, CR 3 R 4 , BR 9 , wherein R 3 , R 4 , and R 9 are independently represented by hydrogen, Substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstit
  • R 3 , R 4 , and R 9 independently represent a C1-C4 alkyl group or a C6-C10 aryl group.
  • L in the compound is represented by any one of the following formulas 11 to 26:
  • R a -R r each independently represents hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 Alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C30 hetero aryl group, or R a -R r capable of binding to and in adjacent positions to form a ring structure; wherein the substituent is deuterium, halogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C6 cycloalkyl, C6-C18 aryl, C
  • R a -R r each independently represent hydrogen, a C1-C8 alkyl group, or a C6-C10 aryl group.
  • R a -R r each independently represent hydrogen, phenyl or naphthyl.
  • R 11 is hydrogen
  • R 12 is phenyl, biphenyl or naphthyl.
  • R 2 contains the part of formula 27:
  • a 1 represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C30 heteroaryl group,
  • Y represents a single bond or a substituted or unsubstituted C6-C30 arylene group
  • X 1 -X 8 each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl , Substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C6-C30 Aralkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C1-C30 heteroaryl group, or adjacent positions are connected to each other to form a cyclic structure and form a ring with formula 27; Wherein said substitution is substituted by deuterium, halogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C
  • formula (27) is directly bonded to formula 1 through at least one of X 1 to X 8 without being substituted or is bonded to formula 1 through an A1 group.
  • X 1 -X 8 represent hydrogen and at least one of X 1 -X 8 is not substituted and is bonded to Formula 1.
  • the A 1 represents a C6-C10 aryl group, a C1-C10 heteroaryl group, and Y represents a single bond or a C6-C10 arylene group.
  • the A 1 represents a C phenyl group, and Y represents a single bond.
  • the preferred compounds are the following compounds:
  • One of the objectives of the present invention is also to provide an OLED device containing the above-mentioned compound.
  • One of the objectives of the present invention is also to provide an OLED device containing the above-mentioned compound, which can be used as a host material and/or a hole blocking layer material in the light-emitting layer in the OLED device.
  • the present invention provides a dibenzoheterocyclic organic compound containing imidazo[1,2-a]pyridine and its application in organic electroluminescence devices.
  • the compound of the present invention has a higher glass transition temperature, higher optical, electrical, and thermal stability, and higher Eg.
  • the compound of the present invention When used as the main body of the light-emitting layer, it has good hole-electron balance, which is beneficial to improve the life of the device; when used as a hole blocking layer, it is beneficial to reduce the diffusion of excitons and is beneficial to improve the light emission of the device. Efficiency, thereby further reducing energy consumption.
  • reaction solution was cooled to room temperature, the dioxane was concentrated in vacuo to a solvent-free distillation, 600ml of DCM was added to dissolve the solid, washed with 200ml of water once, the aqueous phase was extracted with 200ml of DCM once, the organic phases were combined, and washed twice with water (200ml each time ), dry the organic phase with and without water MgSO4. Filter through silica gel and rinse with DCM 300ml. Concentrate the organic phase until only about 150ml remains. Add 500ml of n-hexane to crystallize at room temperature for 2h.
  • Synthesis of compound 05/06/07 Refer to the synthesis method and processing method of compound 04, and only need to change the corresponding raw materials.
  • Synthesis of compound 11 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-2 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 12 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-3 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 13 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-4 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 14 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-5 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 18 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-32 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 19-2 Refer to the synthesis method and processing method of compound 16-3, and only need to change the corresponding raw materials.
  • Synthesis of compound 19 Refer to the synthesis method and processing method of compound 16, and only need to change the corresponding raw materials.
  • Synthesis of compound 21 Refer to the synthesis method and processing method of compound 09, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-32 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • Synthesis of compound 22-2 Refer to the synthesis method and processing method of compound 16-3, and only need to change the corresponding raw materials.
  • Synthesis of compound 22 Refer to the synthesis method and processing method of compound 16, and only need to change the corresponding raw materials.
  • Synthesis of compound H 2-49 Refer to the synthesis method and processing method of compound H 2-1, and only need to change the corresponding raw materials.
  • organic electroluminescent devices a 50mm*50mm*1.0mm glass substrate with ITO (100nm) transparent electrodes was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150 degrees and then treated with N2Plasma for 30 minutes.
  • the cleaned glass substrate is mounted on the substrate holder of the vacuum evaporation device.
  • the transparent electrode line side surface is deposited with the compound HATCN in a manner covering the transparent electrode to form a thin film with a thickness of 5nm, and then the evaporation A layer of HTM1 is deposited to form a film with a thickness of 60nm, and a layer of HTM2 is vapor-deposited on the HTM1 film to form a film with a thickness of 10nm.
  • the main material is vapor deposited on the HTM2 film using a co-evaporation mode (compar The compound 1 or the compound of the present invention) and the doped compound (the doped compound 1 or 2), the film thickness is 30 nm, and the ratio of the host material and the doped material is 90%:10%.
  • the hole blocking layer material (5nm, the compound of the present invention or no such layer), ETL film layer (25nm or 30nm (when there is no hole blocking layer)), LiF film layer (1nm), Finally, a layer of metal Al (100nm) is vapor-deposited as an electrode.
  • the device performance test is performed on the above devices.
  • a constant current power supply (Keithley 2400) is used, a fixed current density is used to flow through the light-emitting element, and both the spectral radiation system (CS 2000) is used to test the luminescence spectrum .
  • CS 2000 spectral radiation system
  • organic electroluminescent device a 50mm*50mm*1.0mm glass substrate with ITO (100nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150 degrees and then treated with N2Plasma for 30 minutes. The cleaned glass substrate is mounted on the substrate holder of the vacuum evaporation device.
  • the transparent electrode line side surface is deposited with the compound HATCN in a manner covering the transparent electrode to form a thin film with a thickness of 5nm, and then the evaporation A layer of HTM1 is deposited to form a film with a thickness of 60nm, and then a layer of HTM2 is deposited on the HTM1 film to form a film with a thickness of 10nm, and then the host material compound A is deposited on the HTM2 film by co-evaporation mode
  • the host material B (comparative compound 1 or the compound of the present invention) and the doped compound 1 have a film thickness of 30 nm, and the ratio of the host material A, the host material B and the doped material is 45%: 45%: 10%.
  • the hole barrier layer material (5nm, comparative compound 1 or the compound of the present invention or no such layer), ETL film layer (25nm or 30nm (when there is no hole barrier layer)), LiF film layer (1nm), and finally a layer of metal Al (100nm) is vapor deposited as an electrode.
  • the compound of the present invention is used as a host material for the light-emitting layer alone, a mixed host material, a hole blocking layer material, or as a host material and a hole blocking layer material at the same time.
  • the organic electroluminescent device as a doping agent exhibits superior performance in driving voltage, luminous efficiency, and device lifetime compared to the comparative compound. It has the potential to be applied to the OLED industry.
  • the compound of the present invention has the advantages of high light and electrochemical stability, high luminous efficiency, long device life, etc., and can be used in organic electroluminescent devices. Especially as a light-emitting host material or/and a hole blocking layer material, it has the potential to be applied to the OLED industry.

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Abstract

本发明涉及一种化合物和含该化合物的有机电致发光器件。该化合物的结构如式(1)所示，其中X选自由以下组成的群组：O、S、Se、CR3R4、SiR 5R6、GeR7R8、BR9。可以用于有机发光器件，特别是用作器件发射层中的主体材料或者空穴阻隔层材料或同时用作二者，可以提供较高的器件发光效率，尤其具有较长的器件寿命等优点，具有应用于AMOLED产业的可能。

Description

一种化合物和含该化合物的有机电致发光器件 技术领域
本发明涉及有机电致发光技术领域，特别涉及一种咪唑并[1,2-a]吡啶的二苯并杂环有机化合物及其在有机电致发光器件上的应用。
背景技术
目前，作为新一代显示技术的有机电致发光器件(OLED)在显示和照明技术方面都获得了越来越多的关注，应用前景十分广泛。但是，和市场应用要求相比，OLED器件的发光效率、驱动电压、使用寿命等性能还需要继续加强和改进。
一般来说，OLED器件基本结构为在金属电极中间夹杂各种不同功能的有机功能材料薄膜，犹如一个三明治的结构，在电流的驱动下，从阴阳两极分别注入空穴和电子，空穴和电子在移动一段距离后，在发光层得到复合，并以光或热的形式进行释放，从而产生了OLED的发光。然而，有机功能材料是有机电致发光器件的核心组成部分，材料的热稳定性、光化学稳定性、电化学稳定性、量子产率、成膜稳定性、结晶性、色饱和度等都是影响器件性能表现的主要因素。
一般地，有机功能材料包括荧光材料和磷光材料。荧光材料通常为有机小分子材料，一般只能利用25％单重态发光，所以发光效率比较低。而磷光材料由于重原子效应引起地自旋轨道耦合作用，除了利用25％单重态之外，还可以利用75％三重态激子的能量，所以发光效率可以得到提升。但是相较于荧光材料，磷光材料起步较晚，同时在使用的过程中，一般采用主体材料与之搭配的方式进行，以利于最大化利用磷光材料的性能。这就对主体材料以及发光层临近的有机薄膜层如空穴阻隔、电子阻隔层材料提出了更高的需求。选择与开发性能更高的OLED功能材料或材料组合，从而达到器件的高效率、低电压、长寿命的性能，是一个具有挑战性的课题。US9780313公开了咪唑并[1,2-a]吡啶与咔唑相联的化合物在OLED器件中用作单一主体，但是器件的效率和寿命，表现不甚理想，有待进一步改进。
发明内容
针对现有技术中存在的上述问题，发明人提供了一种包含咪唑并[1,2-a]吡啶的二苯并杂环有机化合物及其在有机电致发光器件上的应用。本发明的化合物具有较高的玻璃态转变温度和较高的光、电、热稳定性，用于OLED器件时，可提供提高的器件发光效率和寿命以及较低的启动电压，具有应用于OLED产业的可能。
为达到上述目的，本发明采用如下技术方案：
一种包含咪唑并[1,2-a]吡啶的二苯并杂环有机化合物，其中所述有机化合物的结构如式1所示：
Figure PCTCN2020116334-appb-000001
其中X选自由以下组成的群组：O、S、Se、CR 3R 4、SiR 5R 6、GeR 7R 8、BR 9；
其中R 1、R 2、R 11、R 12为无取代到最大可能数目取代，代表多取代时，2个相邻取代能相互连接以与式(1)形成并环结构；
其中R 1-R 9每次出现独立的选自氢、氘、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，且R 2不为氢；
其中R 11-R 12每次出现独立的选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C6-C30芳烷基、取代的或未取代的C1-C10烷氧基、取代的或未取代的C6-C30芳氧基、氨基、取代的或未取代的C3-C30硅烷基、取代的或未取代的C6-C30芳基、取代的或未取代的C1-C30杂芳基、氰基、腈、异腈、膦基；
其中，R 3和R 4、R 5和R 6、R 7和R 8之间能直接键联或通过O、Si、NR 3键联以形成并环；
其中L每次出现独立的选自直接与式(1)相联、取代的或未取代的C1-C10亚烷基、取代的或未取代的C1-C10亚杂烷基、取代的或未取代的C6-C30亚芳烷基、取代的或未取代的C1-C10亚烷氧基、取代的或未取代的C6-C30亚芳氧基、亚氨基、取代的或未取代的C3-C30亚硅烷基、取代的或未取代的C6-C30亚芳基、取代的或未取代的C2-C30亚杂芳基或亚膦基；
其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳基取代的胺基取代。
作为优选的化合物，化合物选自以下式2至9中的任一个；
Figure PCTCN2020116334-appb-000002
Figure PCTCN2020116334-appb-000003
优选R 1为氢，R 2为一取代或相邻的二取代，其中一取代为取代的或未取代的C6-C20的芳基、取代的或未取代的C1-C20的杂芳基，其中二取代为取代的或未取代的C1-C8的烷基、取代的或未取代的C2-C8的烯基、取代的或未取代的C6-C10的芳基、取代的或未取代的C1-C10的杂芳基之间键接成环；
R 11为氢或为一取代或二取代，其中一取代为取代的或未取代的C6-C20的芳基、取代的或未取代的C1-C20的杂芳基，其中二取代为取代的或未取代的C1-C8的烷基、取代的或未取代的C2-C8的烯基、取代的或未取代的C6-C10的芳基、取代的或未取代的C1-C10的杂芳基之间键接成环；R 12为C6-C10的芳基、C1-C10的杂芳基。
优选：所述杂芳基为N杂芳基，其中X选自由以下组成的群组：O、S、CR 3R 4、BR 9，其中R 3、R 4、R 9独立地表示为氢、取代的或未取代的C1-C8的烷基、取代的或未取代的C3-C8环烷基、取代的或未取代的C1-C8的杂烷基、取代的或未取代的C6-C10的芳烷基、取代的或未取代的C6-C10的芳基。
优选：其中R 3、R 4、R 9独立地表示为C1-C4的烷基或C6-C10的芳基。
作为优选的化合物，化合物中L由以下式11至26中的任一个表示：
Figure PCTCN2020116334-appb-000004
Figure PCTCN2020116334-appb-000005
其中，R a-R r各自独立地表示氢、氘、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基、或R a-R r能在相邻位置结合以形成并环结构；其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳基取代的胺基取代。
优选R a-R r各自独立地表示氢、C1-C8的烷基、或C6-C10的芳基。
优选R a-R r各自独立地表示氢、苯基或萘基。
优选：R 11为氢；R 12为苯基、联苯基或萘基。
作为优选的化合物为R 2含有式27的部分：
Figure PCTCN2020116334-appb-000006
其中，A 1表示取代或未取代C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，
Y表示单键或取代或未取代C6-C30的亚芳基；
其中，X 1-X 8各自独立地表示氢、氘、卤素、氰基、羧基、硝基、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，或相邻位置相互连接形成环状结构并与式27形成并环；其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳基取代的胺基取代；
其中式(27)通过X 1-X 8至少之一不被取代而直接键联在式1上或者通过A1基团键联在式1上。
其中X 1-X 8表示氢且X 1-X 8至少之一不被取代而键联在式1上。
所述A 1表示C6-C10的芳基、C1-C10的杂芳基，Y表示单键或C6-C10的亚芳基。
所述A 1表示C苯基，Y表示单键。
作为优选的化合物为以下化合物：
Figure PCTCN2020116334-appb-000007
Figure PCTCN2020116334-appb-000008
Figure PCTCN2020116334-appb-000009
Figure PCTCN2020116334-appb-000010
Figure PCTCN2020116334-appb-000011
本发明的目的之一还在于提供一种含有上述化合物的OLED器件。
本发明的目的之一还在于提供一种含有上述化合物的OLED器件，在OLED器件中用作发光层中主体材料和/或空穴阻隔层材料。
本发明提供了一种包含咪唑并[1,2-a]吡啶的二苯并杂环有机化合物及其在有机电致发光器件上的应用。本发明的化合物具有较高的玻璃态转变温度和较高的光、电、热稳定性以及较高的Eg。本发明的化合物用作发光层主体时，具有较好的空穴电子平衡性，有利于提升器件的寿命；用作空穴阻隔层时，有利于降低激子的扩散，有利于提升器件的发光效率，从而进一步降低能耗。
具体实施例(合成和器件实施)：
所述实施例仅仅是为了便于理解技术发明，不应视为本发明的具体限制。
本发明中的化合物合成中涉及的原物料和溶剂等均购自于Alfa、Acros等本领域技术人 员熟知的供应商。
实施例1：
共用中间体的合成：
Figure PCTCN2020116334-appb-000012
化合物03的合成：向一个2L单口瓶，依次将化合物01(53.17g，0.57mol，1.0eq)、化合物02(200g，0.57mol，1.0eq)，NaHCO 3(94.9g，1.14mol，2.0eq)、异丙醇(1000ml)投入到烧瓶中，油浴加热到80度左右，保温搅拌回流7h，取样TLC监控原料反应完。降温，滴加去离子水，搅拌4h左右，抽滤。固体用乙醇打浆，抽滤烘干。得到157g白色固体化合物03，收率79.6％。质谱：349.03(M+H)
化合物04的合成：向一个1L单口瓶，依次加入化合物03(60g，171.81mmol，1.0eq)、双联频呐硼酸酯(56.72g，223.35mmol，1.3eq)、Pd(dppf)Cl 2(1.26g，1.72mmol，0.01eq)、CH 3COOK(33.72g，343.62mmol，2.0eq)，600ml二氧六环，搅拌下N2置换3次，加热，回流3h。TLC监测反应完全(EA/Hex＝1:8)。反应液降至室温，真空浓缩二氧六环至无溶剂馏出，加入600mlDCM将固体溶解，用水200ml洗一次，将水相用200ml DCM萃取一次，合并有机相，并用水洗两次(每次200ml)，将有机相有无水MgSO4干燥。过硅胶滤，并用DCM 300ml淋洗，浓缩有机相至仅剩150ml左右，加入正己烷500ml降至室温结晶2h。过滤，滤饼用正己烷100ml，淋洗，抽干得到59g，真空干燥过夜，得到54g类白色固体化合物04，收率78.2％。质谱：397.30(M+H)
Figure PCTCN2020116334-appb-000013
化合物05/06/07的合成：参照化合物04的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-1的合成：
Figure PCTCN2020116334-appb-000014
化合物09的合成：
向一个1L三口烧瓶，依次加入化合物08(30g，106.5mmol，1.0eq)、化合物04(38.01g，95.9mmol，0.9eq)，Pd(PPh 3) 4(2.46g，2.13mmol，0.02eq)、K 2CO 3(29.45g，213.12mmol，2.0eq)，甲苯(300ml)，乙醇(60ml)，H 2O(60ml)，抽真空，氮气置换3次，油浴加热到80℃左右，搅拌8h，取样TLC监控原料04反应完。降至室温，加入去离子水(100ml)，搅拌0.5h左右，分液，水相用甲苯萃取1次，合并有机相再水洗两次(100ml/次)，并用无水MgSO 4干燥有机相30min。将有机相过硅胶滤(200-300目，30g)，并用甲苯150ml淋洗。浓缩有机相至剩120ml左右，加入甲醇180ml，常温搅拌析晶2h。过滤，滤饼用30ml甲醇淋洗，抽干，将固体再重复上述方法重结晶1次(甲苯120ml，甲醇180ml)，所得产品烘干后，得到38.2g类白色固体化合物09，收率76.3％。质谱：471.5(M+H)
化合物H 2-1的合成：
向一个1L三口烧瓶，依次加入化合物09(38g，80.69mmol，1.0eq)、化合物10(23.17g，80.69mmol，1.0eq)，Pd-132(0.857g，1.21mmol，0.015eq)、Cs 2CO 3(52.58g，161.38mmol，2.0eq)，甲苯(400ml)，抽真空，氮气置换3次，油浴加热到110℃左右，搅拌8h，取样TLC监控原料基本反应完。降至室温，加入去离子水(150ml)，搅拌0.5h左右，分液，水相用甲苯萃取1次，合并有机相再水洗两次(150ml/次)，并用无水MgSO 4干燥有机相30min。将有机相过硅胶滤(200-300目，40g)，并用甲苯200ml淋洗。浓缩有机相至剩200ml左右，加入甲醇240ml，常温搅拌析晶2h。过滤，滤饼用50ml甲醇淋洗，抽干，将固体再重复上述方法重结晶2次(甲苯200ml，甲醇240ml)，所得产品烘干后，得到29.09g白色固体化合物H2-1，收率53.2％。质谱：678.3(M+H)
1H NMR(400MHz,CDCl 3)δ8.55(d,1H),8.48(d,1H),8.34(s,1H),8.30(d,2H),8.07(s,1H),7.84(d,2H),7.69(d,1H),7.64(t,J＝2.4Hz,1H),7.60(dq,J＝10.0,5.0Hz,5H),7.53(m,2H),7.49(dd,J＝15.0,10.0Hz,7H),7.25(m,2H),7.18(d,J＝25.0Hz,1H),7.11(d,2H),6.86(m,1H).
化合物H 2-2的合成：
Figure PCTCN2020116334-appb-000015
化合物11的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-2的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-3的合成：
Figure PCTCN2020116334-appb-000016
化合物12的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-3的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-4的合成：
Figure PCTCN2020116334-appb-000017
化合物13的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-4的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-5的合成：
Figure PCTCN2020116334-appb-000018
化合物14的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-5的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-32的合成：
Figure PCTCN2020116334-appb-000019
化合物16-3的合成：
向一个1L三口烧瓶，依次加入化合物16-1(75g，250.92mmol，1.0eq)、化合物04(41.56g，238.37mmol，0.95eq)，Pd(dppf)Cl 2(9.18g，12.55mmol，0.05eq)、K 2CO 3(69.36g，501.83mmol，2.0eq)，1,4-二氧六环(450ml)，H 2O(90ml)，抽真空，氮气置换3次，油浴加热到60～70℃，搅拌4h，取样TLC监控原料16-2反应完。降至室温，加入去离子水(150ml)，搅拌0.5h左右，分液，水相用乙酸乙酯(150ml)萃取1次，合并有机相再水洗两次(100ml/次)，分液，有机相旋干。干燥后的粗品进行柱层析分离(流动相为EA：Hex＝1:20)，烘干后得到化合物16-3产品54.85g，收率72.5％。质谱：301.9(M+H)
化合物16的合成：
在2L的三口烧瓶中，先加入NaH(含量60％，14.54g，363.4mmol，2.0eq)和GaH干燥过的无水DMF(270ml)，真空、氮气置换3次，开启搅拌；接着滴加16-3(54.8g，181.73mmol，1.0eq)的无水DMF(530ml)溶液，用时20min滴加完毕，维持室温搅拌30min.；然后将体系加热至120℃搅拌过夜，TLC监控原料16-3已基本反应完全，将体系降至室温，加入200ml冰水萃灭反应，70℃减压浓缩除去DMF，加入1L的EA，去离子水洗涤(3*600ml)，pH为8；减压浓缩有机相得到黄褐色粘稠液体，进行柱层析分离(流动相为EA：Hex＝1:30)，得到白色固体产品化合物16共33.26g，收率65％。质谱：281.5(M+H)
1H NMR(400MHz,CDCl 3)δ7.92(d,1H),7.38(d,1H),7.33(d,1H),7.22(m,1H),7.11(m,J＝4.5Hz,2H).
Figure PCTCN2020116334-appb-000020
化合物18的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-32的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-45的合成：
Figure PCTCN2020116334-appb-000021
化合物19-2的合成：参照化合物16-3的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物19的合成：参照化合物16的合成方式和处理方法，只需要将对应的原物料变更即可。
Figure PCTCN2020116334-appb-000022
化合物21的合成：参照化合物09的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-32的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物H 2-49的合成：
Figure PCTCN2020116334-appb-000023
化合物22-2的合成：参照化合物16-3的合成方式和处理方法，只需要将对应的原物料变更即可。
化合物22的合成：参照化合物16的合成方式和处理方法，只需要将对应的原物料变更即可。
Figure PCTCN2020116334-appb-000024
化合物H 2-49的合成：参照化合物H 2-1的合成方式和处理方法，只需要将对应的原物料变更即可。
选取对应的原物料，用同样类似的方法可以用于合成、升华得到其他化合物。
应用例1：
有机电致发光器件的制作：将50mm*50mm*1.0mm的具有ITO(100nm)透明电极的玻璃基板在乙醇中超声清洗10分钟，再150度烘干后经过N2Plasma处理30分钟。将洗涤后的玻璃基板安装在真空蒸镀装置的基板支架上，首先再有透明电极线一侧的面上按照覆盖透明电极的方式蒸镀化合物HATCN，形成膜厚为5nm的薄膜，紧接着蒸镀一层HTM1形成膜厚为60nm的薄膜，再在HTM1薄膜上蒸镀一层HTM2形成膜厚为10nm的薄膜，然后，在HTM2膜层上再采用共蒸镀的模式蒸镀主体材料(对比化合物1或本发明化合物)和参杂化合物(掺杂化合物1或2)，膜厚为30nm，主体材料和参杂材料比例为90％：10％。在发光层上再依次蒸镀空穴阻隔层材料(5nm,本发明化合物或无此层)、ETL膜层(25nm或30nm(当无空穴阻隔层时))、LiF膜层(1nm)，最后蒸镀一层金属Al(100nm)作为电极。
Figure PCTCN2020116334-appb-000025
评价：将上述器件进行器件性能测试，在各实施例和比较例中，使用恒定电流电源(Keithley2400),使用固定的电流密度流过发光元件，使用分光辐射俩都系(CS 2000)测试发光波谱。 同时测定电压值以及测试亮度为初始亮度的90％的时间(LT90)。结果如下表一：
表一：
Figure PCTCN2020116334-appb-000026
应用例2：
有机电致发光器件的制作：将50mm*50mm*1.0mm的具有ITO(100nm)透明电极的玻璃基板在乙醇中超声清洗10分钟，再150度烘干后经过N2Plasma处理30分钟。将洗涤后的玻璃基板安装在真空蒸镀装置的基板支架上，首先再有透明电极线一侧的面上按照覆盖透明电极的方式蒸镀化合物HATCN，形成膜厚为5nm的薄膜，紧接着蒸镀一层HTM1形成膜厚为60nm的薄膜，再在HTM1薄膜上蒸镀一层HTM2形成膜厚为10nm的薄膜，然后，在HTM2膜层上再采用共蒸镀的模式蒸镀主体材料化合物A、主体材料B(对比化合物1或本发明化合物)和掺 杂化合物1，膜厚为30nm，主体材料A、主体材料B和参杂材料比例为45％：45％：10％。在发光层上再依次蒸镀空穴阻隔层材料(5nm,对比化合物1或本发明化合物或无此层)、ETL膜层(25nm或30nm(当无空穴阻隔层时))、LiF膜层(1nm)，最后蒸镀一层金属Al(100nm)作为电极。
评价：将上述器件进行器件性能测试，在各实施例和比较例中，使用恒定电流电源(Keithley 2400),使用固定的电流密度流过发光元件，使用分光辐射俩都系(CS 2000)测试发光波谱。同时测定电压值以及测试亮度为初始亮度的90％的时间(LT90)。结果如下表二：
表二：
Figure PCTCN2020116334-appb-000027
由上面表一和表二中的数据对比可知，不管是作为单独作为发光层的主体材料、混合主体材料、空穴阻隔层材料或同时作为主体材料和空穴阻隔层材料，使用本发明的化合物作为参杂剂的有机电致发光器件，相较于对比化合物在驱动电压、发光效率、器件寿命都表现出更加优越的性能。具有应用于OLED产业的可能。
上述结果表明本发明的化合物具有光、电化学稳定性高，发光效率高，器件寿命长等优点，可用于有机电致发光器件中。特别是作为发光主体材料或/和空穴阻隔层材料，具有应用于OLED产业的可能。

Claims (18)

  1. 一种包含咪唑并[1,2-a]吡啶的二苯并杂环有机化合物，其中所述有机化合物的结构如式1所示：
    Figure PCTCN2020116334-appb-100001
    其中X选自由以下组成的群组：O、S、Se、CR 3 R 4、SiR 5R 6、GeR 7 R 8、BR 9；
    其中R 1、R 2、R 11、R 12为无取代到最大可能数目取代，代表多取代时，2个相邻取代能相互连接以与式(1)形成并环结构；
    其中R 1-R 9每次出现独立的选自氢、氘、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，且R 2不为氢；
    其中R 11-R 12每次出现独立的选自氢、氘、卤素、取代的或未取代的C1-C10烷基、取代的或未取代的C1-C10杂烷基、取代的或未取代的C6-C30芳烷基、取代的或未取代的C1-C10烷氧基、取代的或未取代的C6-C30芳氧基、氨基、取代的或未取代的C3-C30硅烷基、取代的或未取代的C6-C30芳基、取代的或未取代的C1-C30杂芳基、氰基、腈、异腈、膦基；
    其中，R 3和R 4、R 5和R 6、R 7和R 8之间能直接键联或通过O、Si、NR 3键联以形成并环；
    其中L每次出现独立的选自直接与式(1)相联、取代的或未取代的C1-C10亚烷基、取代的或未取代的C1-C10亚杂烷基、取代的或未取代的C6-C30亚芳烷基、取代的或未取代的C1-C10亚烷氧基、取代的或未取代的C6-C30亚芳氧基、亚氨基、取代的或未取代的C3-C30亚硅烷基、取代的或未取代的C6-C30亚芳基、取代的或未取代的C2-C30亚杂芳基或亚膦基；
    其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳基取代的胺基取代。
  2. 根据权利要求1所述的化合物，选自以下式2至9中的任一个；
    Figure PCTCN2020116334-appb-100002
    Figure PCTCN2020116334-appb-100003
  3. 根据权利要求2所述的化合物，其中R 1为氢，R 2为一取代或相邻的二取代，其中一取代为取代的或未取代的C6-C20的芳基、取代的或未取代的C1-C20的杂芳基，其中二取代为取代的或未取代的C1-C8的烷基、取代的或未取代的C2-C8的烯基、取代的或未取代的C6-C10的芳基、取代的或未取代的C1-C10的杂芳基之间键接成环；
    其中R 11为氢或为一取代或二取代，其中一取代为取代的或未取代的C6-C20的芳基、取代的或未取代的C1-C20的杂芳基，其中二取代为取代的或未取代的C1-C8的烷基、取代的或未取代的C2-C8的烯基、取代的或未取代的C6-C10的芳基、取代的或未取代的C1-C10的杂芳基之间键接成环；R 12为C6-C10的芳基、C1-C10的杂芳基。
  4. 根据权利要求3所述的化合物，所述杂芳基为N杂芳基，其中X选自由以下组成的群组：O、S、CR 3 R 4、BR 9，其中R 3、R 4、R 9独立地表示为氢、取代的或未取代的C1-C8的烷基、取代的或未取代的C3-C8环烷基、取代的或未取代的C1-C8的杂烷基、取代的或未取代的C6-C10的芳烷基、取代的或未取代的C6-C10的芳基。
  5. 根据权利要求4所述的化合物，其中R 3、R 4、R 9独立地表示为C1-C4的烷基或C6-C10的芳基。
  6. 根据权利要求2所述的化合物，其中L由以下式11至26中的任一个表示：
    Figure PCTCN2020116334-appb-100004
    Figure PCTCN2020116334-appb-100005
    其中，R a-R r各自独立地表示氢、氘、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基、或R a-R r能在相邻位置结合以形成并环结构；其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳基取代的胺基取代。
  7. 根据权利要求6所述的化合物，其中R a-R r各自独立地表示氢、C1-C8的烷基、或C6-C10的芳基。
  8. 根据权利要求7所述的化合物，其中R a-R r各自独立地表示氢、苯基或萘基。
  9. 根据权利要求8所述的化合物，其中R 11为氢；R 12为苯基、联苯基或萘基。
  10. 根据权利要求3-9任一所述的化合物，为优选的化合物为R 2含有式27的部分：
    Figure PCTCN2020116334-appb-100006
    其中，A 1表示取代或未取代C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，
    Y表示单键或取代或未取代C6-C30的亚芳基；
    其中，X 1-X 8各自独立地表示氢、氘、卤素、氰基、羧基、硝基、取代的或未取代的C1-C30的烷基、取代的或未取代的C2-C30的烯基、取代的或未取代的C2-C30的炔基、取代的或未取代的C3-C30环烷基、取代的或未取代的C1-C10的杂烷基、取代的或未取代的C6-C30的芳烷基、取代的或未取代的C6-C30的芳基、取代的或未取代的C1-C30的杂芳基，或相邻位置相互连接形成环状结构并与式27形成并环；；其中所述取代为被氘、卤素、C1-C4烷基、C1-C4烷氧基、C3-C6环烷基、C6-C18芳基、C1-C18杂芳基、C1-C4烷基取代的胺基、或C6-C18芳 基取代的胺基取代，
    其中式(27)通过X 1-X 8至少之一不被取代而直接键联在式1上或者通过A1基团键联在式1上。
  11. 根据权利要求10所述的化合物，其中X 1-X 8表示氢且X 1-X 8至少之一不被取代而键联在式1上。
  12. 根据权利要求11所述的化合物，所述A 1表示C6-C10的芳基、C1-C10的杂芳基，Y表示单键或C6-C10的亚芳基。
  13. 根据权利要求12所述的化合物，所述A 1表示C苯基，Y表示单键。
  14. 根据权利要求1-9任一所述的化合物，为下列化合物之一：
    Figure PCTCN2020116334-appb-100007
    Figure PCTCN2020116334-appb-100008
    Figure PCTCN2020116334-appb-100009
    Figure PCTCN2020116334-appb-100010
    Figure PCTCN2020116334-appb-100011
  15. 根据权利要求1-14任一所述的化合物在有机电致发光器件中的应用。
  16. 一种有机电致发光器件，其包含至少一层安放在阴极和阳极之间的发光层或电子传输层之间的空穴阻隔层，其中权利要求1-14任一项所述的化合物位于发光层和/或空穴阻隔层。
  17. 根据权利要求16所述的有机电致发光器件，其中发光层材料包含主体材料和磷光掺杂剂，其中所述权利要求1-14任一项所述的化合物用作主体材料。
  18. 根据权利要求17所述的有机电致发光器件，所述主体材料包含多种主体化合物，其中所述第一主体为权利要求1-14任一项所述的化合物，且第二主体为含有3,3’-联咔唑部分的化合物。
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