CN108794404B - 一种蒽类有机发光化合物及其制备方法以及有机电致发光器件 - Google Patents

一种蒽类有机发光化合物及其制备方法以及有机电致发光器件 Download PDF

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CN108794404B
CN108794404B CN201810691248.5A CN201810691248A CN108794404B CN 108794404 B CN108794404 B CN 108794404B CN 201810691248 A CN201810691248 A CN 201810691248A CN 108794404 B CN108794404 B CN 108794404B
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organic
anthracene
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CN108794404A (zh
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马晓宇
李文军
黄悦
刘静
张颖
刘天娇
王辉
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

本发明提供了一种蒽类有机发光化合物，具有式Ⅰ所示结构。本发明提供的新型蒽类有机发光化合物作为有机电致发光器件的电子传输层材料，与其他电子传输层材料相比，发光效率提升明显，寿命改善显著。且所述蒽类有机发光化合物合成路线较短，工艺简单，原料易得，成本低，适合工业化生产。

Description

一种蒽类有机发光化合物及其制备方法以及有机电致发光 器件
技术领域
本发明涉及有机光电材料技术领域，尤其涉及一种蒽类有机发光化合物及其制备方法以及有机电致发光器件。
背景技术
有机电致发光(EL)是指有机材料在电场作用下，将电能直接转化为光能的一种发光现象。其具有自发光、颜色鲜艳亮丽、厚度薄、质量轻、响应速度快、视角广、驱动电压低、耐受苛刻自然条件、可做成柔性面板等特点，逐渐发展成为新一代平板显示领域最具优势技术。
关于有机电致发光器件(OEL)即有机发光二极管(OLED)的研究起始于上世纪50年代。一般的有机电致发光器件是由阴极、阳极和位于二者之间的有机物层构成的。一般阳极为透明ITO，阴极由LiAl等组成。其中的有机层包括空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、发光层(EL)、空穴阻挡层(HBL)、电子传输层(ETL)、电子注入层(EIL)。两个电极之间形成电压，一边从阴极注入电子，另一边从阳极注入空穴，注入的电子和空穴在发光层再结合，其电子状态从基态转向激发态。因为激发态极其不稳定，激发态又回到稳定的基态。这时，能量被释放，表现为光的形式。
有机EL材料自发明以来，因其相对于前两代显示(CRT以及LCD)器具有明显的优势，被产业广泛的应用。但因其效率以及寿命等因素制约了其发展。在有机材料中，电子和空穴的转移速度是不同的，若使用适合的材料，将电子和空穴有效的转移到发光层，平衡电子和空穴的数量，可有效的提高发光效率。
随着市场对有机EL器件要求不断的提高，具有高效率、长寿命的器件成为了发展趋势。然而适合的材料十分难于寻找。三(8-羟基喹啉)铝(Alq3)作为电子传输材料自发明以来使用了将近30年，而且有较多的资料证明其比常规材料优异。但其作为电子传输材料，有向其他层移动等因素制约了其应用。因此开发一种符合实用性要求的新型电子传输材料成为了迫切需求。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种蒽类有机发光化合物及其制备方法以及有机电致发光器件，具有较高的发光效率和寿命。
本发明提供的蒽类有机发光化合物，具有式Ⅰ所示结构：
Figure BDA0001712546890000021
在本发明的一些具体实施例中，所述蒽类有机发光化合物具有式Ⅰ-a所示结构：
Figure BDA0001712546890000022
其中，R1和R2独立的优选为以下任一基团：
氢、卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
取代或非取代的硅基、硼烷基或磷基；
取代或非取代的C1～C60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
取代或非取代的C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
进一步，R1和R2独立的优选为：取代或非取代的C3～C30环烷基、C1～C30杂环基、C6～C30芳基、C7～C30的芳烷基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基或C10～C30的稠环基。
更进一步，R1和R2独立的优选为：取代或非取代的C3～C20环烷基、C1～C20杂环基、C6～C20芳基、C7～C20的芳烷基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基或C10～C20的稠环基。
本发明中，所述R1和R2均不为三嗪基和蒽基。
R3优选为取代或非取代的C1～C60的烷基、C3～C60的环烷基、C1～C60的杂环基、C6～C60芳基、C7～C60的芳烷基、C8～C60的芳烯基、C2～C60的杂芳基、C10～C60的稠环基或C10～C60的螺环基。
进一步，R3优选为取代或非取代的C3～C30的环烷基、C1～C30的杂环基、C6～C30芳基、C7～C30的芳烷基、C2～C30的杂芳基或C10～C30的稠环基。
更进一步，R3优选为取代或非取代的C3～C20的环烷基、C1～C20的杂环基、C6～C20芳基、C7～C20的芳烷基、C2～C20的杂芳基或C10～C20的稠环基。
上述取代的R1、R2和R3的取代基团独立的优选为：
卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～30的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C30的环烷基；
C6～C30的芳基、C7～C30的芳烷基、C8～C30的芳烯基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基、C10～C30的稠环基、C6～C30芳基取代的硅基或C2～C30杂芳基取代的硅基。
更进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～20的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C20的环烷基；
C6～C20的芳基、C7～C20的芳烷基、C8～C20的芳烯基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基、C10～C20的稠环基、C6～C20芳基取代的硅基或C2～C20杂芳基取代的硅基。
再进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～10的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C12的环烷基；
C6～C12的芳基、C7～C12的芳烷基、C8～C14的芳烯基、C6～C12的芳胺基或C6～C12的芳巯基、C2～C12的杂芳基、C10～C20的稠环基、C6～C12芳基取代的硅基或C2～C12杂芳基取代的硅基。
在本发明的一些具体实施例中，所述R1、R2和R3独立的选自以下任一基团：
取代或非取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基；
或者2～6个任意以上基团稠合形成的稠环基团；
或者2～6个任意以上基团通过单键、N、O、B、Si、P、P＝O、S或S＝O连接形成的基团；
上述环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的任意一个或多个C原子可被O、S、N或Si取代；
上述基团或取代基团的H原子可被氘代。
上述取代的环戊基、环己基、苯基，吡咯基、噻吩基或呋喃基的取代基团优选为：
卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～60的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C60的环烷基；
C6～C60的芳基、C7～C60的芳烷基、C8～C60的芳烯基、C6～C60的芳胺基或C6～C60的芳巯基、C2～C60的杂芳基、C10～C60的稠环基、C6～C60芳基取代的硅基或C2～C60杂芳基取代的硅基。
进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～30的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C30的环烷基；
C6～C30的芳基、C7～C30的芳烷基、C8～C30的芳烯基、C6～C30的芳胺基或C6～C30的芳巯基、C2～C30的杂芳基、C10～C30的稠环基、C6～C30芳基取代的硅基或C2～C30杂芳基取代的硅基。
更进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～20的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C20的环烷基；
C6～C20的芳基、C7～C20的芳烷基、C8～C20的芳烯基、C6～C20的芳胺基或C6～C20的芳巯基、C2～C20的杂芳基、C10～C20的稠环基、C6～C20芳基取代的硅基或C2～C20杂芳基取代的硅基。
再进一步优选为卤素、氰基、硝基、羟基、氨基、磺酸基、磺酰基、磷酸基或磷酰基；
C1～10的烷基、烷氧基、烷胺基、烷巯基、杂环基或C3～C12的环烷基；
C6～C12的芳基、C7～C12的芳烷基、C8～C14的芳烯基、C6～C12的芳胺基或C6～C12的芳巯基、C2～C12的杂芳基、C10～C20的稠环基、C6～C12芳基取代的硅基或C2～C12杂芳基取代的硅基。
在本发明的另外一些具体实施例中，所述R1、R2和R3独立的优选为以下任一基团，或者2个以上任意基团由单键连接形成的基团：
Figure BDA0001712546890000051
其中，X和Y独立的优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C30的烷基、C3～C30的环烷基、C1～C30的烷氧基、C2～C30的烯基、C7～C30的烷芳基、C7～C30的烷芳氧基、C6～C30的芳基、C6～C30的芳氧基、C2～C30的杂环基、C5～C30的杂芳基或C6～C30的芳香族胺；
进一步优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C20的烷基、C3～C20的环烷基、C1～C20的烷氧基、C2～C20的烯基、C7～C20的烷芳基、C7～C20的烷芳氧基、C6～C20的芳基、C6～C20的芳氧基、C2～C20的杂环基、C5～C20的杂芳基或C6～C20的芳香族胺。
更进一步优选为氢原子、卤素原子、氰基、硝基、羟基、氨基、取代或未取代的C1～C10的烷基、C3～C12的环烷基、C1～C10的烷氧基、C2～C10的烯基、C7～C20的烷芳基、C7～C20的烷芳氧基、C6～C20的芳基、C6～C20的芳氧基、C2～C12的杂环基、C5～C20的杂芳基或C6～C20的芳香族胺。
所述Q为C或N。
所述P为C、N、O或S。
所述Z为O或S。
上述取代基结构式中的弯线表示连接位置。
当上述2个以上任意基团由单键连接形成基团时，本发明对单键连接的位置并无特殊限定，也并不局限于上述弯线标注的连接位置，可以为C原子与C原子，C原子与杂原子或杂原子与杂原子之间的任意连接。
本发明所述的2～6个任意以上基团稠合形成的稠环基团或者2个以上任意基团由单键、N、O、B、Si、P、P＝O、S或S＝O连接形成的基团中，相同基团可出现一次或多次，如两个苯基稠合形成萘基，或者两个苯基通过单键分别与吡咯基连接，或者3个苯基通过B原子相连接，或者苯基通过N原子与吡啶基相连接等。
在本发明的另外一些具体实施例中，所述蒽类有机发光化合物具有以下具体结构：
Figure BDA0001712546890000071
Figure BDA0001712546890000081
Figure BDA0001712546890000091
Figure BDA0001712546890000101
Figure BDA0001712546890000111
Figure BDA0001712546890000121
上述化合物结构式中的单键表示甲基。
本发明还提供了上述蒽类有机发光化合物的制备方法，包括以下步骤：
式Ⅱ所示化合物和式Ⅲ所示化合物进行缩合反应，得到式Ⅳ所示化合物；
式Ⅳ所示化合物经溴化，得到式Ⅴ所示化合物；
式Ⅴ所示化合物和R1-B(OH)2反应，得到式Ⅰ所示化合物；
Figure BDA0001712546890000131
上述R1、R2和R3的范围同上，在此不再赘述。
上述反应的反应路线如下：
Figure BDA0001712546890000141
在本发明的一些具体实施例中，所述制备方法具体包括以下步骤：
步骤1：将三(二亚苄基丙酮)二钯和三环己基膦加入到干燥的1,4-二氧六环溶剂中，在室温下活化一段时间。向反应液中加入中间体1-a、联硼酸频那醇酯以及醋酸钾。将反应液加热反应。
反应结束后，优选的，利用硅藻土除去盐以及催化剂，减压蒸馏滤液至少许，滴加至石油醚中析出。待固体析出完全，抽滤、烘干，得到中间体如式Ⅱ所示。
Figure BDA0001712546890000151
步骤2：将2-溴蒽、式2-a、缚酸剂加入到甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基磷)钯，再次用氮气置换空气三次，在氮气保护下加热反应。
待反应结束后，优选的，使用硅藻土除去催化剂，分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:5)得到中间体。
Figure BDA0001712546890000152
步骤3：将中间体2-b加入到DMF溶剂中，加入NBS，将反应液加热反应。
反应结束后，优选的，将反应液浓缩至少许，滴加至石油醚中析出。待固体析出完全，抽滤，烘干，得到中间体如式Ⅲ所示；
Figure BDA0001712546890000153
步骤4：将中间体式Ⅲ、与式Ⅱ所示化合物、碳酸钾加入到300ml甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基磷)钯，在氮气保护下加热反应。
反应结束后，优选的，使用硅藻土除去催化剂。分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:10)得到中间体如式Ⅳ所示；
Figure BDA0001712546890000161
步骤5：将中间体式Ⅳ加入到DMF溶剂中，加入NBS，将反应液加热反应。
反应结束后，优选的，减压蒸馏至少许溶液，滴加至石油醚中析出。待固体析出完全，抽滤，烘干，得到中间体如式Ⅴ所示。
Figure BDA0001712546890000162
步骤6：将中间体式Ⅴ、R1-B(OH)2、碳酸钾加入到甲苯/乙醇/水(体积比优选3:1:1)的混合溶剂中。加入四(三苯基磷)钯，在氮气保护下加热到90℃,反应12h。
反应结束后，优选的，使用硅藻土除去催化剂。分液，保留有机相，减压蒸馏至少量。将所得粗品使用柱层析色谱进行分离(洗脱剂优选DCM:PE＝1:5)，得到式Ⅰ所示目标化合物；
Figure BDA0001712546890000163
本发明提供了一种有机电致发光器件，包括上述蒽类有机发光化合物或上述制备方法制备的蒽类有机发光化合物。
所述有机电致发光器件为本领域技术人员熟知的有机电致发光器件即可，本发明优选包括第一电极、第二电极和设置于所述第一电极与第二电极之间的一个或多个有机物层；至少一个所述有机物层包含上述蒽类有机发光化合物。
本发明中，所述有机物层是指有机电致发光器件第一电极和第二电极之间的全部层。所述有机物层中的至少一层为发光层。
按照本发明，所述有机物层优选包括空穴注入层、空穴传输层、同时具备空穴注入和空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层与同时具备电子传输和电子注入技能层中的一层或多层，更优选包括依次设置的空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层与电子注入层或依次设置的既具备空穴注入又具备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层与既具备电子传输又具备电子注入技能层。
当本发明有机物层包含空穴注入层、空穴传输层和同时具备空穴注入和空穴传输技能层时，优选所述空穴注入层、空穴传输层和同时具备空穴注入和空穴传输技能层中至少一层包含空穴注入物质、空穴传输物质或既具备空穴注入又具备空穴传输技能的物质。
当本发明有机物层为单层结构时，所述有机物层为发光层，当所述有机物层为多层结构时，所述有机物层包括发光层；所述发光层中优选包括磷光主体、荧光主体、磷光掺杂材料与荧光掺杂材料中的一种或多种。
当所述有机物层包括电子传输层时，所述电子传输层可包括式(I)所示的蒽类有机发光化合物。在本发明的一些具体实施例中，所述电子传输层还包括金属化合物。所述金属化合物为本领域技术人员熟知的用于电子传输的物质即可，并无特殊的限制。
当所述有机物层同时包括发光层与电子传输层时，所述发光层与电子传输层可分别包括结构相同或不相同的式(I)所示的蒽类有机发光化合物。
本发明提供的有机电致发光器件，利用式(I)所示的蒽类有机发光化合物及常规材料制成即可，本发明对所述有机电致发光器件的制备方法并无限定，本领域常规方法即可，本发明优选利用薄膜蒸镀、电子束蒸发或物理气相沉积等方法在基板上蒸镀金属及具有导电性的氧化物及它们的合金形成阳极，然后在其上形成有机物层及蒸镀阴极，得到有机电致发光器件。
所述有机物层可以同时包括上述的空穴注入层、空穴传输层、发光层、空穴阻挡层及电子传输层的多层结构，并且这些多层结构可按照上述薄膜蒸镀、电子束蒸发或物理气相沉积等方法蒸镀，也可使用多样的高分子材料溶剂工程替代蒸镀方法，如旋转涂膜(spin-coating)、薄带成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等方法减少层数制造。
本发明提供的有机电致发光器件按照使用的材料也可分为前面发光、背面发光或两面发光；并且该有机电致发光器件可以同样原理应用在有机发光器件(OLED)、有机太阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)上。
本发明提供的式(I)所示的蒽类有机发光化合物在有机太阳电池、照明用OLED、柔性OLED、有机感光体及有机晶体管等有机器件中也可按照适用有机发光器件的原理适用。
本发明还提供了一种有机光电材料，包括上述式(I)所示的蒽类有机发光化合物；所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
与现有技术相比，本发明提供了一种蒽类有机发光化合物，具有式Ⅰ所示结构。本发明提供的新型蒽类有机发光化合物作为有机电致发光器件的电子传输层材料，与其他电子传输层材料相比，发光效率提升明显，寿命改善显著。且所述蒽类有机发光化合物合成路线较短，工艺简单，原料易得，成本低，适合工业化生产。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明提供的蒽类有机发光化合物及其制备方法以及有机电致发光器件进行详细描述。
实施例1
中间体C-1的合成：
Figure BDA0001712546890000181
反应过程：将2-溴蒽(20.0g，77.8mmol)、苯硼酸(11.38g，93.34mmol)、碳酸钾(32.25g，233.34mmol)加入到500ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基磷)钯(0.9g，0.78mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温。使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:5)得到中间体C-1(16.81g，yield＝85％)。
按照上述方法制备得到表1所示中间体。
表1实施例1反应原料以及产物结构及表征汇总
Figure BDA0001712546890000182
Figure BDA0001712546890000191
实施例2
中间体D-1的合成
Figure BDA0001712546890000192
反应过程：将中间体C-1(16.5g，64.88mmol)加入到200ml DMF溶剂中，加入NBS(13.86g，77.86mmol)，将反应液加热到50℃。
处理过程：TLC监测反应。反应结束后，将反应液浓缩至少许，缓慢滴加到搅拌的石油醚中。待固体析出完全，抽滤，烘干，得到中间体D-1(19.45g，yield＝90％)。
按照上述方法制备得到表2所示中间体。
表2实施例2反应原料以及产物结构及表征汇总
Figure BDA0001712546890000201
Figure BDA0001712546890000211
实施例3
中间体G-1的合成
Figure BDA0001712546890000212
反应过程：将三(二亚苄基丙酮)二钯(1.05g，1.145mmol)和三环己基膦(0.8g，2.86mmol)加入到干燥的1,4-二氧六环溶剂中，用氮气置换空气三次，在室温下活化30分钟。向反应液中加入E-1(20.0g，57.27mmol)、联硼酸频那醇酯(17.45g，68.724mmol)以及醋酸钾(22.45g，229.08mmol)。用氮气置换空气三次，将反应液加热到100℃。
处理过程：TLC监测反应。反应结束后，在氮气保护下冷却至室温。利用硅藻土除去催化剂，用二氯甲烷冲洗滤饼至无产品。浓缩滤液至少许，边搅拌将将浓缩液滴加至石油醚中。待固体析出完全，抽滤、烘干，得到中间体G-1(19.06g，收率84％)。
按照上述方法制备得到表3所示中间体。
表3实施例3反应原料以及产物结构及表征汇总
Figure BDA0001712546890000213
Figure BDA0001712546890000221
实施例4
中间体H-1的合成
Figure BDA0001712546890000231
反应过程：将中间体D-1(16.6g，49.8mmol)、G-1(19.0g，49.8mmol)、碳酸钾(20.6g，149.4mmol)加入到300ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基磷)钯(0.58g，0.5mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温，使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:10)得到中间体H-1(20.27g，收率78％)。
按照上述方法制备得到表4所示中间体。
表4实施例4反应原料以及产物结构及表征汇总
Figure BDA0001712546890000232
Figure BDA0001712546890000241
实施例5
中间体I-1的制备
Figure BDA0001712546890000251
反应过程：将中间体H-1(20.0g，38.2mmol)加入到200ml DMF溶剂中，加入NBS(13.6g，76.4mmol)，将反应液加热到50℃。
处理过程：TLC监测反应。反应结束后，将反应液浓缩至少许，缓慢滴加到搅拌的石油醚中。待固体析出完全，抽滤，烘干，得到中间体I-1(19.5g，收率85％)。
按照上述方法制备得到表5所示中间体。
表5实施例5反应原料以及产物结构及表征汇总
Figure BDA0001712546890000252
Figure BDA0001712546890000261
实施例6目标化合物的制备
Figure BDA0001712546890000271
反应过程：将中间体I-1(19.5g，32.42mmol)、苯硼酸(5.92g，48.63mmol)、碳酸钾(13.4g，97.26mmol)加入到500ml甲苯/乙醇/水(体积比3:1:1)的混合溶剂中。使用氮气置换空气三次，加入四(三苯基磷)钯(0.49g，0.32mmol)，再次用氮气置换空气三次，在氮气保护下加热到90℃。
处理过程：TLC监测。待反应结束后，在氮气保护下冷却至室温。使用分液漏斗进行分液，保留有机相。使用硅藻土除去催化剂，用DCM洗硅藻土至无产品。浓缩滤液至少量，硅胶拌样，使用硅胶漏斗进行分离(DCM:PE＝1:5)得到目标化合物K-1(16.87g，收率87％)。
按照上述方法制备得到表6所示中间体。
表6实施例6反应原料以及产物结构及表征汇总
Figure BDA0001712546890000272
Figure BDA0001712546890000281
Figure BDA0001712546890000291
本发明以上述化合物为例，其余化合物的制备同上，在此不再赘述。
实施例7
有机电致发光器件制备
将费希尔公司涂层厚度为
Figure BDA0001712546890000293
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀厚度为50nm的4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)作为空穴注入层。在形成的空穴注入层上面真空蒸镀厚度为30nm的N'-二(1-萘基)-N,N'-二苯基-(1,1'-联苯)-4,4'-二胺(a-NPD)作为空穴传输层。然后在上述空穴传输层上蒸镀厚度为30nm的蓝色主体材料9,10-二(2-萘基)蒽(AND)和掺杂材料N1,N1,N6,N6-四苯基芘-1,6-二胺(TPPDA)。主体材料和掺杂材料的重量比为95:5。接着在上述发光层上真空蒸镀厚度为10nm的双(2-甲基-8-羟基喹啉-N1,08)-(1,1’-联苯-4-羟基)铝(BAlq)作为空穴阻挡层。在上述空穴阻挡层上真空蒸镀厚度为40nm的如表6所示的本发明制备的化合物中的任意一种，作为电子传输层。在上述电子传输层上真空蒸镀厚度为0.5nm氟化锂(LiF)，作为电子注入层。最后蒸镀厚度为150nm的铝作为阴极，以此完成了有机电致发光器件的制备。
对上述制备的有机电致发光器件加以正向直流偏置电压，利用Photo Research公司的PR-650光度测量设备测定有机电致发光特性，并在5000cd/m2的基准灰度下利用McScience公司的寿命测定装置测定了T95的寿命。结果见表7。
比较例1
按照实施例7相同的方法制备有机电致发光器件，电子传输层化合物结构如下：
Figure BDA0001712546890000292
对制备的有机电致发光器件进行与实施例7相同的检测，结果见表7。
表7实施例7以及比较例1中有机电致发光器件检测结果
Figure BDA0001712546890000301
从上述表7结果中可以看出，使用本发明提供的化合物作为电子传输层所制备的有机电致发光器件，与使用比较例化合物Alq3作为电子传输层所制备的有机电致发光器件相比，驱动电压以及电流密度明显降低，发光效率以及寿命得到显著提高。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (4)

1.一种蒽类有机发光化合物，具有式I所示结构：
Figure FDA0002512899520000011
所述式I选自以下结构：
Figure FDA0002512899520000012
Figure FDA0002512899520000021
Figure FDA0002512899520000031
2.一种权利要求1所述的蒽类有机发光化合物的制备方法，包括以下步骤：
式Ⅱ所示化合物和式Ⅲ所示化合物进行缩合反应，得到式Ⅳ所示化合物；
式Ⅳ所示化合物经溴化，得到式Ⅴ所示化合物；
式Ⅴ所示化合物和R1-B(OH)2反应，得到式I所示化合物；
Figure FDA0002512899520000032
或包括以下步骤：
式2所示化合物和式Ⅲ所示化合物进行反应，得到式4所示化合物；
式4所示化合物经溴化，得到式5所示化合物；
式5所示化合物和式6所示化合物反应，得到式I所示化合物；
Figure FDA0002512899520000041
3.一种有机电致发光器件，包括权利要求1所述的蒽类有机发光化合物或权利要求2所述的制备方法制备的蒽类有机发光化合物。
4.一种有机光电材料，其特征在于，包括权利要求1所述的蒽类有机发光化合物或权利要求2所述的制备方法制备的蒽类有机发光化合物；所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
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