CN108117539A - 一种有机电致发光化合物、有机电致发光器件及其应用 - Google Patents

一种有机电致发光化合物、有机电致发光器件及其应用 Download PDF

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CN108117539A
CN108117539A CN201711429834.4A CN201711429834A CN108117539A CN 108117539 A CN108117539 A CN 108117539A CN 201711429834 A CN201711429834 A CN 201711429834A CN 108117539 A CN108117539 A CN 108117539A
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organic electroluminescent
organic
electroluminescent compounds
layer
electrode
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金振禹
钱超
王晓维
戴培培
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Nanjing Topto Materials Co Ltd
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Nanjing Topto Materials Co Ltd
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Abstract

本发明提供了一种有机电致发光化合物、有机电致发光器件及其应用。本发明有机电致发光化合物结构如下其中，R1,R2和R4分别独立为氢，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；R3为C1～C10的烷基，或者C6～C30的芳基；R5为氢，氘，卤素，C1～C20的直链或支链烷基，或者C6～C30芳基；R6，R7分别独立的为氢，氘，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；X独立的为碳或氮；I是0～4的整数；m、n分别独立为0或1。本发明有机电致发光化合物不仅能够有效降低器件工作电压，同时还提高器件的发光效率和使用寿命。

Description

一种有机电致发光化合物、有机电致发光器件及其应用
技术领域
本发明涉及发光材料领域，具体而言，涉及一种有机电致发光化合物、有机电致发光器件及其应用。
背景技术
随着OLED技术在照明和显示两大领域的不断推进，人们对于影响OLED器件性能的高效有机材料的研究也更加关注。作为新颖的平面显示技术，自OLED显示展现了其作为自发光器件的优异显示性能以来，在世界范围都对其进行了积极的研究。同时，由于器件机构简单而易于制造，也使其能够用于制造超薄和超轻的显示器。在最常见的OLED器件结构中，通常包括以下种类的有机材料：空穴注入材料、空穴传输材料、电子传输材料，以及各色的发光材料(染料或者掺杂客体材料)和相应的主体材料等。
有机电致发光器件一般由基板、阳极、从阳极接收空穴的空穴注入层、用于传输空穴的空穴传输层、阻止电子发光层进入到空穴传输层的电子阻隔层、空穴和电子相结合而发光的发光层、组织空穴从发光层进入到电子传输层的空穴阻隔层，以及从阴极接收电子的电子注入层以及阴极所构成。其驱动原理如下：向阳极和阴极之间施加电压时，从阳极注入的空穴就要经由空穴注入层和空穴传输层移动到发光层。同时，电子从阴极经由电子注入层和电子传输层注入到发光层，在发光层中与载流子再结合而形成激子。激子在此状态下变化为基态，由此，发光层的荧光性分子发光，形成画像。此时，激发态通过单重激发态回到基态，所发出来的光叫做“荧光”；通过三重激发态回到基态，所发出来的光叫做“磷光”。通过单重激发态回到基态的概率为25％，通过三重激发态回到基态的概率为75％，因此，发光效率有限；使用磷光的话，三重态75％和单重激发态25％都可以用来发光，理论上来说，内部量子效率可以达到100％。这种有机电致发光器件最大的问题是使用寿命短和发光效率低，随着显示屏的大面积化，使用寿命短和发光效率低成为必须要解决的问题。
目前，空穴传输材料和发光主体材料多为芳香多胺类化合物或具有咔唑骨架的化合物，主要是三芳胺类衍生物，如NPB、TPD、TCTA、TNATA、铜酞菁(CuPc)。虽然这些材料在发光性质方面具有优势，但是有机电致发光器件的发光效率与电流效率成正比，与驱动电压成反比，目前使用现有有机材料的发光器件，需要较高的驱动电压，导致有机电致发光器件的发光效率低，该发光效率仍不能令人满意。
因此，迫切需要开发一种能够提高器件发光效率的有机电致发光化合物。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种有机电致发光化合物，所述的有机电致发光化合物能够有效降低器件工作电压，同时提高器件的发光效率和使用寿命。
本发明的第二目的在于提供一种有机电致发光器件，所述有机电致发光器件包含本发明有机电致发光化合物，因而具有高效率和长寿命等优异性能。
本发明的第三目的在于提供一种所述的有机电致发光化合物在制备有机电致发光器件中的应用，将本发明有机电致发光化合物应用于有机电致发光器件中，能够提高有机电致发光器件的效率和使用寿命。
为了实现本发明的上述目的，特采用以下技术方案：
一种有机电致发光化合物，所述有机电致发光化合物结构如下：
其中，式(I)中，R1,R2和R4分别独立为氢，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
R3为C1～C10的烷基，或者C6～C30的芳基；R5为氢，氘，卤素，C1～C20的直链或支链烷基，或者C6～C30芳基；R6，R7分别独立的为氢，氘，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；X独立的为碳或氮；I是0～4的整数；m、n分别独立为0或1。
优选的，本发明所述的有机电致发光化合物中，当R1,R2或者R4为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，吡啶基，嘧啶基或者三嗪基时，其中至少一个氢原子被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素，CN,CF3，Si(CH3)3，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基取代或非取代。
优选的，本发明所述的有机电致发光化合物中，当R5为C6～C30的芳基时，其中一个以上的氢被氘，卤素，C1～C10的烷基，C2～C10的烯基，C1～C10的烷氧基，C6～C30的芳基和C5～C30的杂芳基所取代或非取代。
优选的，本发明所述的有机电致发光化合物中，当R6或R7为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，吡啶基，嘧啶基或者三嗪基时，其中至少一个以上的氢被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素，CN,CF3,Si(CH3)3，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基所取代或非取代。
优选的，本发明所述的有机电致发光化合物中，所述化合物为下列化合物1～120中的任意一种：
同时，本发明还提供了一种包含本发明所述的有机电致发光化合物的有机电致发光器件。
优选的，本发明所述的有机电致发光化合物的有机电致发光器件包括：第一电极，面向所述第一电极的第二电极，以及在所述第一电极和第二电极间的有机层，所述有机层包含发光层；其中，所述有机层包含本发明所述的有机电致发光化合物。
优选的，本发明所述的有机电致发光器件中，所述第一电极为阳极，所述第二电极为阴极，并且所述有机层包含选自以下的至少一个：
i)在所述第一电极与所述发光层之间并且包含选自空穴注入层、空穴传输层、发光辅助层和电子阻挡层中的至少一个的空穴传输区；和
ii)在所述发光层与所述第二电极之间并且包括电子传输层和选自缓冲层、空穴阻挡层、电子控制层和电子注入层中的至少一层的电子传输区；
其中，所述发光层包含本发明所述的有机电致发光化合物；和/或，所述空穴传输区包含本发明所述的有机电致发光化合物；和/或，所述电子传输区包含本发明所述的有机电致发光化合物。
进一步的，本发明也提供了包含所述的有机电致发光器件的有机电致发光显示设备。
同样的，本发明还提供了本发明所述的有机电致发光化合物在制备有机电致发光器件中的应用；和/或，本发明所述的有机电致发光化合物在制备有机电致发光显示设备中的应用。
与现有技术相比，本发明的有益效果为：
本发明有机电致发光化合物可作为HTL(空穴传输层)、EBL(电子阻隔层)、B-dopant(发光客体)、Host(发光主体)、EIL(电子注入层)、ETL(电子传输层)、CPL(cappinglayer)材料而应用于有机电致发光器件和相应的显示设备中，能够降低驱动电压，提高发光效率、亮度、热稳定性、色彩纯度及器件寿命。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
有鉴于，现有有机电致发光化合物在发光效率和使用寿命等方面所存在着的不足，本发明特提供了一种新型有机电致发光化合物，从而解决现有化合物在实际使用性能上的不足，并进一步实现相应的器件和设备使用性能的提高。
具体的，本发明所提供的有机电致发光化合物结构如下：
其中，式(I)中，R1,R2和R4分别独立为氢，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
其中，当R1,R2和R4中任意的R基为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基时，该所述的苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基上的一个或两个及以上的氢原子可以被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素(优选的为F、Cl、Br、I)，CN(腈基),CF3(三氟甲基)，Si(CH3)3(三甲基硅基)，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基所取代，从而形成取代或者非取代结构的苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
R3为C1～C10的烷基，或者C6～C30的芳基；
R5为氢，氘，卤素，C1～C20的直链或支链烷基，或者C6～C30芳基；
其中，当R5为C6～C30的芳基时，该所述C6～C30的芳基上的一个或两个及以上的氢原子可以被氘，卤素，C1～C10的烷基，C2～C10的烯基，C1～C10的烷氧基，C6～C30的芳基和C5～C30的杂芳基所取代；从而形成取代或者非取代结构的C6～C30的芳基；
R6，R7分别独立的为氢，氘，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
其中，当R6或R7中任意的R基为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，吡啶基，嘧啶基或者三嗪基时，该所述的苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基上的一个或两个及以上的氢原子可以被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素，CN,CF3,Si(CH3)3，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基所取代，从而形成取代或者非取代结构的苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
X独立的为碳或氮；
I是0～4的整数，例如，I可以为0,1,2,3，或者4；
m、n分别独立为0或1。
而如上式(I)结构的有机电致发光化合物可以作为HTL(空穴传输层)、EBL(电子阻隔层)、B-dopant(发光客体)、Host(发光主体)、EIL(电子注入层)、ETL(电子传输层)、CPL(capping layer)材料而应用于有机电致发光器件和相应的显示设备中，从而起到提高发光效率、使用寿命等性能的目的。
实施例1化合物(55)的合成
(1)中间体A的合成
[反应式1]
将19.5g(100mmol，1.0eq.)吖啶酮和20.4g碘苯(100mmol，1.0eq.)投入干燥的2L三口烧瓶中，再加入干燥并除气过的800ml甲苯作溶剂，通氮气15分钟。再加入28.8g(300mmol.3.0eq.)叔丁醇钠，1.8g(2％mol)催化剂Pd2(dba)3和8.1ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至100℃，反应过夜5小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到22.5g的中间体A，产率在83％。
(2)中间体B的合成
[反应式2]
将22.5g(83mmol,1.0eq.)中间体A投入到1L的三口烧瓶中，用400mlDMF作溶剂，再在室温避光条件下加入12.0g(91.3mmol，1.1eq.)NBS，室温避光反应18小时。带反应结束，加入饱和Na2SO3溶液，析出大量固体，搅拌1小时，抽滤，用水多次冲洗，再用乙醇冲洗1次，干燥后用甲苯和乙醇重结晶，得到23.0g中间体B，产率79％。
(3)中间体C的合成
[反应式3]
将实验装置充分干燥，在3L三口烧瓶中加入15.3g(65.7mml,1.0eq.)2-溴联苯，加入200ml干燥过得四氢呋喃，溶解后降温至-78℃,滴加28.7ml2.5M(71.6mmol,1.2eq.)的n-BuLi。滴加结束后在该温度下搅拌1小时，再在该温度下滴加23g(65.7mmol,1.0eq.)中间体B，滴加结束后室温搅拌过夜。待反应结束，加水搅拌1小时，静置分层，有机相用水洗三次，滤液用二氯甲烷萃取并水洗，合并有机相，干燥，旋除溶剂，充分干燥，再投料到2L的干燥三口烧瓶中，加入600ml乙酸和150ml浓盐酸，升温至110℃，回流过夜16小时，结束反应。冷却至室温，加入适量水，搅拌，析出固体，抽滤，水洗滤饼，再用乙醇打浆3次，最后干燥，得到21.1g中间体C，产率为66％。
(4)中间体D的合成
[反应式4]
将21.1g(43.4mmol,1.0eq)中间体C和12.1g(47.7mmol，1.1eq.)联硼酸频那醇酯投入在干燥的2L三口烧瓶中，再加入干燥并除气过的700ml甲苯作溶剂，通氮气15分钟，加入0.3g催化剂Pd(dppf)2Cl2(3％mol)和12.8g(130.2mmol,3.0eq.)乙酸钾。升温至110℃，反应过夜15小时。待反应结束，冷却至室温，加活性炭，过硅胶短柱，旋干滤液，用甲苯和乙醇重结晶，得到19.9g中间体D，产率在86％。
(5)中间体E的合成
[反应式5]
将26.3g(120mmol，1.2eq.)N-苯基-2-萘胺和21.9g 4-溴-4-碘联苯(100mmol，1.0eq.)投入干燥的2L三口烧瓶中，再加入干燥并除气过的1000ml甲苯作溶剂，通氮气15分钟。再加入19.2g(200mmol,2.0eq.)叔丁醇钠，1.8g(2％mol)催化剂Pd2(dba)3和8.1ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至100℃，反应过夜3小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到35.6g中间体E，产率在79％。
(6)化合物55的合成
[反应式6]
将14.8g(37.3mmol,1.1eq.)中间体E和15.3g(33.9mmol，1.0eq.)中间体D，加入到2L的三口烧瓶中，加入600ml甲苯和60ml乙醇溶解，通氮气15分钟，再加入51ml含有14.1gK2CO3(101.7mmol,3.0eq.,2M)的水溶液,最后加入0.8g Pd(PPh3)4(2mol％)。升温至100℃，反应过夜16小时结束。加活性炭吸附，抽滤，旋除溶剂，干燥，用甲苯和乙醇重结晶，得到20.5g化合物55，产率在78％。
1H NMR(DMSO,300Hz):δ(ppm)＝8.07-7.85(d,2H),7.82-7.69(m,3H),7.64-7.51(m,5H),7.49-7.14(m,23H),7.11-6.89(m,7H)；
MS(FAB):776(M+)。
实施例2化合物(72)的合成
(1)中间体F的合成
[反应式6]
将19.5g(100mmol，1.0eq.)吖啶酮和20.4g碘苯(100mmol，1.0eq.)投入干燥的2L三口烧瓶中，再加入干燥并除气过的800ml甲苯作溶剂，通氮气15分钟。再加入28.8g(300mmol)叔丁醇钠，1.8g(2％mol)催化剂Pd2(dba)3和8.1ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至100℃，反应过夜5小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到22.5g中间体F，产率在83％。
(2)中间体G的合成
[反应式7]
将22.5g(83mmol)中间体F投入到1L的三口烧瓶中，用400ml DMF作溶剂，再在室温避光条件下加入12.0g(91.3mmol，1.1eq.)NBS，室温避光反应18小时。带反应结束，加入饱和Na2SO3溶液，析出大量固体，搅拌1小时，抽滤，用水多次冲洗，再用乙醇冲洗1次，干燥后用甲苯和乙醇重结晶，得到23.0g中间体G，产率79％。
(3)中间体H的合成
[反应式8]
将实验装置充分干燥，在3L三口烧瓶中加入17.2g(65.7mml,1.0eq.)2-溴二苯甲酮，加入200ml干燥过得四氢呋喃，溶解后降温至-78℃,滴加31.5ml 2.5M(78.8mmol,1.2eq.)的n-BuLi。滴加结束后在该温度下搅拌1小时，再在该温度下滴加23g(65.7mmol,1.0eq.)中间体G，滴加结束后室温搅拌过夜。待反应结束，加水搅拌1小时，静置分层，有机相用水洗三次，滤液用二氯甲烷萃取并水洗，合并有机相，干燥，旋除溶剂，充分干燥，再投料到2L的干燥三口烧瓶中，加入600ml乙酸和150ml浓盐酸，升温至110℃，回流过夜16小时，结束反应。冷却至室温，加入适量水，搅拌，析出固体，抽滤，水洗滤饼，再用乙醇打浆3次，最后干燥，得到22g中间体H，产率为65％。
(4)中间体I的合成
[反应式9]
在干燥的2L三口烧瓶中加入22g(120mmol，1.2eq.)中间体H和24.7g3-溴苯并二呋喃(100mmol，1.0eq.)，再加入干燥并除气过的900ml甲苯作溶剂，通氮气15分钟。再加入19.2g(200mmol,2.0eq.)叔丁醇钠，1.8g(2％mol)催化剂Pd2(dba)3和8.1ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至100℃，反应过夜3小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到25.5g中间体I，产率在76％。
(5)中间体J的合成
[反应式10]
将26.3g(42.8mmol，1.0eq.)中间体I和14.3g(42.8mmol，1.0eq.)中间体H投入到干燥的2L三口烧瓶中，再加入干燥并除气过的800ml甲苯作溶剂，通氮气15分钟。再加入8.2g(85.6mmol,2.0eq.)叔丁醇钠，0.8g(2％mol)催化剂Pd2(dba)3和3.5ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至100℃，反应过夜3小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到27g中间体J，产率在82％。
(6)中间体K的合成
[反应式11]
将27g(35.1mmol，1.0eq.)中间体J和3.5g(70.2mmol,2.0eq.)一水合肼投入到3L的三口烧瓶中,3.9g(67.1mmol,2.0eq.)KOH,用600ml二乙醇作溶剂，在110℃下反应15小时后，再在195℃下反应6小时。待反应结束，冷却至室温，有大量固体形成，抽滤，水洗，醇洗，在甲苯中重结晶，得到15.9g中间体K，产率60％。
(6)化合物72的合成
[反应式12]
将2g(12.7mmol,0.6eq.)溴苯和3.6g(12.7mmol,0.6eq.)投入到干燥的2L的三口烧瓶中，用100ml THF溶解后降至-78℃，滴加10.1ml(25.3mmol,1.2eq.)2.5M n-BuLi,滴加结束后在-78℃下搅拌1小时，再滴加150ml含15.9g(21.1mmol，1.0eq.)中间体K的THF溶液，滴加结束后转移到室温反应3小时。滴加500ml水淬灭反应，静置分层，上层有机相再用水洗，干燥，旋除溶剂，用甲苯重结晶，得到10.6g化合物72，产率51％。
1H NMR(DMSO,300Hz):δ(ppm)＝8.21-7.95(m,2H),7.91-7.71(m,5H),7.90-7.67(m,41H),6.97-6.84(m,2H)；
MS(FAB):983(M+)。
实施例3化合物(97)的合成
(1)中间体L的合成
[反应式13]
将28.3g(100mmol，1.0eq.)间溴碘苯和20.6g邻溴苯胺(120mmol，1.2eq.)投入到干燥的3L三口烧瓶中，再加入干燥并除气过的1000ml甲苯作溶剂，通氮气15分钟。再加入2.9g(15％mol)碘化亚铜，5.9g(30％mol)1,10-菲啰啉和63.7g(300mol，3eq.)磷酸钾。升温至110℃，反应18小时。待反应结束，冷却至室温，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到28.1g中间体L，产率在86％。
(2)中间体M的合成
[反应式14]
将28.1g(86mmol)中间体L和17.9g(86mmol)的蒽醌投入到2L的三口烧瓶中，加入500ml 32％的HCl，在260℃下反应2小时。待反应结束后，有大量固体，冷却至室温，抽滤，多次水洗，醇洗，干燥后用乙醇打浆2次，抽滤得到产品，干燥得到25.6g中间体M，68％产率。
(3)中间体N的合成
[反应式15]
将25.6g(58.5mmol,1.0eq.)中间体M和5.6g(58.5mmol,1.0eq.)氟苯投料到2L的三口烧瓶中，配置机械搅拌，加入500ml DMF，再缓慢加入38.1g(117mmol，2eq.)碳酸铯。升温至170℃，反应过夜15小时。待反应结束，冷却至室温，抽滤，滤液用水和二氯甲烷萃取，用水多次洗有机相，旋除溶剂，得到的固体用乙醇在室温下打浆3次，抽滤，干燥得到26.5g中间体N，产率在88％.
(4)中间体O的合成
[反应式16]
将26.5g(51.5mmol，1.0eq.)中间体N和21.1g(51.5mmol，1.0eq.)3-(4-联苯基)胺-9-苯基-9H-咔唑投入到干燥的2L三口烧瓶中，再加入干燥并除气过的800ml甲苯作溶剂，通氮气15分钟。再加入9.9g(103mmol,2.0eq.)叔丁醇钠，0.9g(2％mol)催化剂Pd2(dba)3和4.2ml(4％mol)P(t-bu)3的甲苯溶液(m/v，10％)。升温至90℃，反应5小时。待反应结束，冷却至室温，加活性炭吸附，抽滤，旋除溶剂，用甲苯和乙醇重结晶，得到34.3g中间体O，产率在79％。
(5)中间体P的合成
[反应式17]
将34.3g(40.7mmol，1.0eq.)中间体O和4.1g(81.4mmol,2.0eq.)一水合肼投入到3L的三口烧瓶中,4.6g(81.4mmol,2.0eq.)KOH,用600ml二乙醇作溶剂，在110℃下反应15小时后，再在195℃下反应6小时。待反应结束，冷却至室温，有大量固体形成，抽滤，水洗，醇洗，在甲苯中重结晶，得到18.9g中间体P，产率56％。
(6)化合物97的合成
[反应式18]
将2.3g(13.7mmol,0.6eq.)邻溴甲苯和3.7g(13.7mmol,0.6eq.)1-溴-9,9’-二甲基-9H-芴投入到干燥的2L的三口烧瓶中，用100ml THF溶解后降至-78℃，滴加10.9ml(27.4mmol,1.2eq.)2.5M n-BuLi,滴加结束后在-78℃下搅拌1小时，再滴加140ml含18.9g(22.8mmol，1.0eq.)中间体P的THF溶液，滴加结束后转移到室温反应3小时。滴加500ml水淬灭反应，静置分层，上层有机相再用水洗，干燥，旋除溶剂，用甲苯重结晶，得到11.7g化合物97，产率46％。
1H NMR(DMSO,300Hz):δ(ppm)＝8.37-8.15(d,1H),8.06-7.97(s,1H),7.94-7.81(m,3H),7.78-7.69(d,2H),7.67-6.84(m,44H),6.61-6.43(d,1H),2.45-2.21(s,3H),1.78-1.47(s,6H)；
MS(FAB):1112(M+)。
实施例4化合物(116)的合成
(1)中间体Q的合成
[反应式19]
将22.2g(100mmol,1.0eq.)10,10-二甲基蒽酮投入到1L的三口烧瓶中，用400mlDMF作溶剂，再在室温避光条件下加入19.6g(110mmol，1.1eq.)NBS，室温避光反应18小时。带反应结束，加入饱和Na2SO3溶液，析出大量固体，搅拌1小时，抽滤，用水多次冲洗，再用乙醇冲洗1次，干燥后用甲苯和乙醇重结晶，得到25g中间体Q，产率83％。
(2)中间体R的合成
[反应式20]
将32g(100mmol)四苯基甲烷投入到1L的三口烧瓶中，用600ml DMF作溶剂，再在室温避光条件下加入19.6g(110mmol，1.1eq.)NBS，室温避光反应16小时。带反应结束，加入饱和Na2SO3溶液，析出大量固体，搅拌1小时，抽滤，用水多次冲洗，再用乙醇冲洗1次，干燥后用甲苯和乙醇重结晶，得到31.5g中间体R，产率79％。
(3)中间体S的合成
[反应式21]
将实验装置充分干燥，在2L三口烧瓶中加入31.5g(79mml,1.0eq.)中间体R，加入300ml干燥过得四氢呋喃，溶解后降温至-78℃,滴加37.9ml2.5M(94.8mmol,1.2eq.)的n-BuLi。滴加结束后在该温度下搅拌1小时，再在该温度下滴加200ml含有23.8g(79mmol,1.0eq.)中间体R的四氢呋喃溶液，滴加结束后室温搅拌过夜。待反应结束，加水搅拌1小时，静置分层，有机相用水洗三次，滤液用二氯甲烷萃取并水洗，合并有机相，干燥，旋除溶剂，充分干燥，再投料到2L的干燥三口烧瓶中，加入600ml乙酸和150ml浓盐酸，升温至110℃，回流过夜16小时，结束反应。冷却至室温，加入适量水，搅拌，析出固体，抽滤，水洗滤饼，再用乙醇打浆3次，最后干燥，得到32.9g中间体S，产率为69％。
(4)中间体T的合成
[反应式22]
将32.9g(54.5mmol,1.0eq.)中间体S和15.2g(60mmol，1.1eq.)联硼酸频那醇酯投入到干燥的2L三口烧瓶中，再加入干燥并除气过的1000ml 1,4-二氧六环作溶剂,通氮气15分钟，加入0.4g催化剂Pd(dppf)2Cl2(3％mol)和16g(163.5mmol,3.0eq.)乙酸钾。升温至110℃，反应过夜15小时。待反应结束，冷却至室温，加活性炭，过硅胶短柱，旋干滤液，用甲苯和乙醇重结晶，得到27.7g中间体T，产率在78％。
(5)化合物116的合成
[反应式23]
将27.7g(42.5mmol,1.1eq.)中间体T和18.4g(38.6mmol，1.0eq.)N-(4-溴苯基)-N,N-二-(4-联苯基)胺，加入到2L的三口烧瓶中，加入1000ml甲苯和100ml乙醇溶解，通氮气15分钟，再加入59ml含有16g K2CO3(115.8mmol,3.0eq.,2M)的水溶液,最后加入0.9g Pd(PPh3)4(2mol％)。升温至100℃，反应过夜16小时结束。加活性炭吸附，抽滤，旋除溶剂，干燥，用甲苯和乙醇重结晶，得到26g化合物116，产率在72％。
1H NMR(DMSO,300Hz):δ(ppm)＝7.93-7.71(m,4H),7.68-7.63(s,1H),7.61-7.49(m,10H),7.47-6.92(m,32H),1.81-1.53(s,6H)；
MS(FAB):920(M+)。
同时，参照上述反应式1～23的方法得到化学式1所示1～120中其余的化合物。
实验例1有机电致发光器件的制造
采用ITO作为反射层阳极基板材料，并用N2等离子或UV-Ozone对其进行表面处理。在阳极基板上方，向HIL层沉积厚度的HAT-CN。在上述HTL层上方，选择上述化合物4真空蒸镀形成空穴传输层。在上述空穴传输层上真空蒸镀TCTA形成的电子阻隔层，上述电子阻隔层蒸镀能够形成blue EML的9，10-Bis(2-naphthyl)anthraces(ADN)作为发光层，以dopant掺杂约5％的2,5,8,11-四丁基二萘嵌苯形成的发光层。在其上方将蒽衍生物和Liq以1:1的比例混合蒸镀的厚度到电子传输层，在电子传输层之上蒸镀的Liq作为电子注入层。最后在阴极蒸镀厚度的银。此外，在阴极表面用含有UV硬化性粘合剂吸水材料密封，以保护有机电致发光器件不被大气中的氧气或水分所影响。
本实验例中所涉及到的化合物的结构式如下：
实验例2～12
分别以化合物11、18、34、43、55、65、72、85、97、107和116作为空穴传输层(HTL)物质，其他部分与实施例1一致，据此制作出实验例2～12的有机电致发光器件。
比较例1
上述NPD作为空穴传输层材料代替实验例中使用本发明化合物作为空穴注入材料，其他情况都与实验例1用相同的方法制造有机电致发光器件。
在电流密度为10mA/cm2的条件下，对上述实验例制造的有机电致发光器件1～12及比较例制造的有机电致发光器件进行性能测定，结果如下表1所示。
表1实验例与比较例有机电致发光器件性能对比
从表1的对照检测结果可以得知的是,本发明的实施例1-12的有机电致发光器件与比较例1中所述的现有的有机电致发光器件相比,发光效率性能有明显的改进，且使用本发明的有机化合物作为空穴传输物质时，有机电致发光器件的驱动电压明显降低。本发明的有机化合物可以为有机电致发光器件提供降低电力驱动并减少电力消耗的效果，另外，通过低电力驱动，有机电致发光器件的寿命也会有所提高。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (10)

1.一种有机电致发光化合物，其特征在于，所述有机电致发光化合物结构如下：
其中，式(I)中，R1,R2和R4分别独立为氢，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
R3为C1～C10的烷基，或者C6～C30的芳基；
R5为氢，氘，卤素，C1～C20的直链或支链烷基，或者C6～C30芳基；
R6，R7分别独立的为氢，氘，C1～C20的直链或支链烷基，苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，嘧啶基，或者三嗪基；
X独立的为碳或氮；
I是0～4的整数；
m、n分别独立为0或1。
2.根据权利要求1所述的有机电致发光化合物，其特征在于，当R1,R2或者R4为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，吡啶基，嘧啶基或者三嗪基时，其中至少一个氢原子被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素，CN,CF3，Si(CH3)3，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基取代或非取代。
3.根据权利要求1所述的有机电致发光化合物，其特征在于，当R5为C6～C30的芳基时，其中一个以上的氢被氘，卤素，C1～C10的烷基，C2～C10的烯基，C1～C10的烷氧基，C6～C30的芳基和C5～C30的杂芳基所取代或非取代。
4.根据权利要求1所述的有机电致发光化合物，其特征在于，当R6或R7为苯基，吡啶基，萘基，菲基，蒽基，菲啶基，联苯基，吡啶基，嘧啶基或者三嗪基时，其中至少一个以上的氢被C1～C20的直连或支链烷基，C3～C24的环烷基，C1～C20的烷氧基，卤素，CN,CF3,Si(CH3)3，萘基，蒽基，菲基，苯并呋喃基，二苯并呋喃基，芴基，咔唑基，螺芴基或环原子数为5～20的杂芳基所取代或非取代。
5.根据权利要求1-4中任一项所述的有机电致发光化合物，其特征在于，所述化合物为下列化合物1～120中的任意一种：
6.一种包含权利要求1-5中任一项所述的有机电致发光化合物的有机电致发光器件。
7.根据权利要求6所述的有机电致发光器件，其特征在于，所述有机电致发光器件包括：第一电极，面向所述第一电极的第二电极，以及在所述第一电极和第二电极间的有机层，所述有机层包含发光层；
其中，所述有机层包含权利要求1-5中任一项所述的有机电致发光化合物。
8.根据权利要求7所述的有机电致发光器件，其特征在于，所述第一电极为阳极，所述第二电极为阴极，并且所述有机层包含选自以下的至少一个：
i)在所述第一电极与所述发光层之间并且包含选自空穴注入层、空穴传输层、发光辅助层和电子阻挡层中的至少一个的空穴传输区；和
ii)在所述发光层与所述第二电极之间并且包括电子传输层和选自缓冲层、空穴阻挡层、电子控制层和电子注入层中的至少一层的电子传输区；
其中，所述发光层包含权利要求1-5中任一项所述的有机电致发光化合物；
和/或，所述空穴传输区包含权利要求1-5中任一项所述的有机电致发光化合物；
和/或，所述电子传输区包含权利要求1-5中任一项所述的有机电致发光化合物。
9.一种包含权利要求6-8中任一项所述的有机电致发光器件的有机电致发光显示设备。
10.权利要求1-5中任一项所述的有机电致发光化合物在制备有机电致发光器件中的应用；
和/或，权利要求1-5中任一项所述的有机电致发光化合物在制备有机电致发光显示设备中的应用。
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