CN114957251A - 一种高性能光电材料、制备方法及有机电致发光器件 - Google Patents
一种高性能光电材料、制备方法及有机电致发光器件 Download PDFInfo
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- CN114957251A CN114957251A CN202210749173.8A CN202210749173A CN114957251A CN 114957251 A CN114957251 A CN 114957251A CN 202210749173 A CN202210749173 A CN 202210749173A CN 114957251 A CN114957251 A CN 114957251A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004305 biphenyl Substances 0.000 claims abstract description 3
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- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical class [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 18
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
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- FQENSZQWKVWYPA-UHFFFAOYSA-N dibenzofuran-3-ylboronic acid Chemical compound C1=CC=C2C3=CC=C(B(O)O)C=C3OC2=C1 FQENSZQWKVWYPA-UHFFFAOYSA-N 0.000 claims description 4
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- MWEKPLLMFXIZOC-UHFFFAOYSA-N pyren-1-ylboronic acid Chemical compound C1=C2C(B(O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 MWEKPLLMFXIZOC-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003944 tolyl group Chemical group 0.000 claims description 4
- XSAOVBUSKVZIBE-UHFFFAOYSA-N (9-phenylcarbazol-2-yl)boronic acid Chemical compound C=1C(B(O)O)=CC=C(C2=CC=CC=C22)C=1N2C1=CC=CC=C1 XSAOVBUSKVZIBE-UHFFFAOYSA-N 0.000 claims description 3
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 claims description 3
- MBHPOBSZPYEADG-UHFFFAOYSA-N 2-bromo-9,9-dimethylfluorene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC=CC=C3C2=C1 MBHPOBSZPYEADG-UHFFFAOYSA-N 0.000 claims description 3
- FRNLBIWVMVNNAZ-UHFFFAOYSA-N 2-iodonaphthalene Chemical compound C1=CC=CC2=CC(I)=CC=C21 FRNLBIWVMVNNAZ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
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Abstract
Description
技术领域
本发明涉及一种高性能光电材料、制备方法及有机电致发光器件,属于有机电致发光技术领域。
背景技术
有机电致发光装置是一种自发光装置,其优点在于具有诸如宽视角、优异的对比度、快速响应、高亮度、优异的驱动电压特性的优点,并且能够提供多彩图像。有机电致发光装置最初由伊士曼柯达(Eastman kodak)通过使用小芳香族二胺分子和铝络合物作为用于形成发光层的材料而开发。
典型的OLED结构包括基底及顺序堆叠在基底的阳极、空穴传输层(HTL)、发射层(EML)、电子传输层(ETL)和阴极。当将电压施加到阳极和阴极时,从阳极注入的空穴通过HTL移动到EML,从阴极注入的电子通过ETL移动到EML。电子和空穴在EML中复合以产生激子。当激子的能态从激发态下降到基态时,发射光。
OLED的发光效率可以分类为内部发光效率和外部发光效率。内部发光效率收到诸如HTL、EML和ETL的有机层中激子产生并转换成光的效率的影响。所述有机层设置在第一电极和第二电极之间(即阳极和阴极之间)。另一方面,外部发光效率(光结合效率)受到将在有机层中产生的光从OLED中引出的效率影响。如果外部发光效率低,则即使有机层中的发光效率高(即内部发光效率高),OLED的发光效率也降低。
正在开发的有机电致发光器件用于许多不同种类的电子应用。例如在手机、手表、电视中都有良好应用。然而,对于将这些器件用于高质量和长寿命的显示器,仍然需要进一步改进。通常期望寿命、效率和电压的进一步改进。更具体地,为了在高温下使用,高玻璃化转变温度对于实现长寿命是必不可少的。有机发光材料的性质通常是有机电致发光器件的寿命和效率的限制因素,需要使用新型材料进一步改良有机发光元件的发光效率。
发明内容
本发明针对现有技术存在的不足,提供一种高性能光电材料、制备方法及有机电致发光器件,所述光电材料具有高的热稳定性,,高的玻璃化转变温度,使用本发明的光电材料化合物作为主体发光材料的有机电致发光元件拥有更高的发光效率及更长的寿命。
本发明解决上述技术问题的技术方案如下:一种高性能光电材料,所述的光电材料为嘧啶并菲啶类化合物,所述光电材料的化学结构通式为:
其中,Ar为氘代或未被氘代的苯基、联苯基、三联苯基、萘基、9-苯基蒽基、芘基、菲基、苯并蒽基、二苯并呋喃基、二苯并噻吩基、9,9-二甲基芴基、9,9-二苯基芴基、9-苯基二苯并咔唑基、3,5-二苯基三嗪基。
进一步的,所述Ar选自如下结构:
进一步的,所述光电材料选自如下化合物:
本发明还公开了所述高性能光电材料的制备方法,所述的制备方法为:
S1、化合物A的制备:
在有机溶剂中加入6-溴喹唑啉,在一定温度下,滴加正丁基锂正己烷溶液,然后控制反应温度,滴加DMF,反应毕,经后处理得到化合物A;
S2、化合物B的制备:
在有机溶剂中,化合物A、2-溴-4-氯-苯胺和对甲苯磺酸混合后,加热反应,反应毕,经过后处理得到化合物B;
S3、化合物C的制备:
在惰性气体保护下,化合物B、碳酸铯、THF、醋酸钯和三环己基膦混合后,升温回流反应,反应毕,经后处理得到化合物C;
S4、化合物D的制备:
在惰性气体保护下,化合物C、联硼酸频哪醇酯、乙酸钾、Pd(dba)2、三环己基膦、二氧六环混合,加热反应,反应毕,经后处理得到化合物D;
S5、化合物E的制备:
以化合物C和芳基硼酸为主要原料,化合物C和芳基硼酸,碳酸钾、水,钯催化剂加入到有机溶剂中,碳酸钾水溶液提供碱性环境,控温反应温度进行反应,反应毕,经后处理得到化合物E;
或者,以化合物D和卤代芳烃为主要原料,化合物D和卤代芳烃,碳酸钾,水,四(三苯基膦)钯,加入到有机溶剂中,碳酸钾水溶液提供碱性环境,控温反应温度进行反应,反应毕,经后处理得到化合物E;
所述的X为Cl、Br或I。
进一步的,步骤S5中,所述芳基硼酸为苯硼酸、2-联苯硼酸、2-三联苯硼酸、2-萘硼酸、1-芘硼酸、3-二苯并呋喃硼酸、9,9-二甲基-1-芴硼酸、N-苯基-2-咔唑硼酸、9,9-二苯基-2-芴硼酸。
进一步的,步骤S5中,所述卤代芳烃为氯苯,碘苯,溴苯,1-溴萘,2-碘萘,3-溴二苯并呋喃,9-溴菲,2-溴-9,9-二甲基芴,3-溴-N-苯基咔唑,4-氯联。
进一步的,步骤S5中,以化合物C和芳基硼酸为主要原料时,反应温度为70~80℃,反应时间为12~24h,有机溶剂为甲苯;
以化合物D和卤代芳烃为主要原料时,反应温度为70~80℃,反应时间为12~24h,有机溶剂为甲苯。
本发明还公开了一种有机电致发光器件,所述的有机电致发光器件中含有本发明所述光电材料的一种或至少两种组合。
进一步的,所述有机电致发光器件包括阳极、阴极以及夹在阳极与阴极之间的有机薄膜层,所述的有机薄膜层包括发光层。
进一步的,所述发光层中含有本发明所述光电材料的一种或至少两种组合。
本发明的有益效果是:
(1)本发明所述光电材料具有较高的热稳定性,较高的玻璃化转变温度,而且所述的光电材料化合物是可升华的,摩尔质量几乎都小于1000g/mol,升华后可去除所述化合物中的无机杂质,避免制成器件影响器件性能。这些光电材料的物化性质,使其在有机电致发光器件中具有更好的应用;
(2)本发明所述光电材料化合物结构中嘧啶机构和菲啶结构结合后,形成主链共轭的分子构型,这种构型借助于嘧啶并菲啶基团密集的电子分布以及基团之间紧密的堆积,电荷可通过载流子在基团之间的跳跃来实现高效的传递,带来良好的光电性能。含有至少三个或更多氮原子或至少一个具有相对高电子迁移率的取代基能够使电子更好进行传输,本发明在此基础上,多耦合一个刚性结构的苯环,可以提高化合物的热稳定性及化学稳定性,使其具有优秀的荧光发射能力并应用于发光层中。
(3)本发明所述光电材料可以提高有机电致放光器件的发光效率,使用本发明所述光电材料制备的OLED具有非常长的寿命。
附图说明
图1为应用例1中所述有机电致发光器件的结构示意图。
图中,1、基底;2、ITO;3、空穴注入层;4、为空穴传输层;5、发光层;6、电子传输层;7、电子注入层;8、阴极反射电极层。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似改进,因此本发明不受下面公开的具体实施例的限制。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。
其中初始原料6-溴喹唑啉和2-溴-4-氯苯胺均为购买,中间体化合物以A、B、C、D表示,最终产物以E表示;其中X为Cl、Br或I。
1、化合物A制备方法:
于反应器中加入6-溴喹唑啉10.0g(47.8mmol)、四氢呋喃100ml,控温-78.0℃以下,滴加22.9ml(57.4mmol)正丁基锂正己烷溶液(2.5M),滴加毕于-78.0℃以下保温0.5h,然后控温-78.0℃以下滴加DMF 7g(95.6mmol),滴毕于-78.0℃以下控温反应,保温3h跟踪TLC反应至主原料6-溴喹唑啉反应无剩余,合格后经水解,乙酸乙酯萃取水洗,过硅胶层析柱,浓缩,粗品经2倍乙酸乙酯重结晶烘干后得到目标产物A 6.3g,收率84%,HPLC:99.1%,1H NMR:δ8.17-8.34(2H,8.23(dd,J=8.3,1.2Hz),8.27(dq,J=8.3,0.5Hz)),8.56(1H,ddd,J=1.5,1.2,0.5Hz),8.91(1H,dd,J=1.9,0.5Hz),9.33(1H,ddd,J=1.9,1.5,0.5Hz),10.09(1H,s).
元素分析结构:分子式为C9H6N2O;LC-MS产物分子量:158.05。
2、化合物B制备方法:
以化合物A和2-溴-4-氯-苯胺为主原料,反应瓶中加入化合物A 6.3g(39.8mmol)、2-溴-4-氯-苯胺8.2g(39.8mmol)、甲苯44g、对甲苯磺酸0.27g(1.59mmol),料加毕,控温145℃反应,反应4h取样跟踪TLC无化合物A剩余,反应合格后浓缩、乙酸乙酯溶解过硅胶柱得到目标产物B13g HPLC(化合物B 51.49%+异构44.01%):95.5%,收率94.2%。1H NMR:δ7.25-7.49(3H,7.31(dd,J=8.3,0.5Hz),7.33(dd,J=1.8,0.5Hz),7.42(dd,J=8.3,1.8Hz)),8.14-8.33(2H,8.20(dd,J=6.5,1.4Hz),8.27(dq,J=6.5,0.5Hz)),8.51(1H,td,J=1.4,0.5Hz),8.84-9.04(2H,8.89(dd,J=2.0,0.5Hz),8.99(s)),9.31(1H,ddd,J=2.0,1.4,0.5Hz).
元素分析结构:分子式为C15H9BrClN3;LC-MS检测产物分子量:345.02;
3、化合物C制备方法:
向充有氮气的250ml三口瓶中加入化合物B13g(37.5mmol)、碳酸铯24.5g(75mmol)、THF 78g、醋酸钯0.336g(1.5mmol)、三环己基膦0.84g(3mmol),升温至60~65℃回流保温反应,保温24h取样跟踪TLC无化合物B剩余,反应合格后经水解、水洗、脱溶剂、1倍甲苯重结晶得到目标产物C 8g,HPLC:99.26%,收率80.3%。1H NMR:δ7.96-8.15(2H,8.02(dt,J=8.4,0.5Hz),8.09(dd,J=8.4,1.6Hz)),8.27(1H,dq,J=8.7,0.5Hz),8.56(1H,dd,J=8.7,1.9Hz),8.90-9.06(2H,8.96(dd,J=1.6,0.4Hz),9.00(dd,J=1.9,0.6Hz)),9.48(1H,dd,J=1.9,0.6Hz),9.60(1H,dt,J=1.9,0.5Hz).
元素分析结构:分子式为C15H8ClN3;LC-MS检测产物分子量:265.04。
4、化合物D的制备方法:
以化合物C为原料,向充有氮气的250ml三口瓶中加入化合物C 8g(30mmol)、联硼酸频哪醇酯8.8g(34.6mmol)、乙酸钾5.9g(60mmol)、Pd(dba)2 0.17g(0.3mmol)、三环己基膦0.17g(0.6mmol)、二氧六环80g(77ml),搅拌升温至100~110℃,控温90~100℃保温5hTLC判断无化合物C剩余,反应合格后经萃取、水洗、过柱、脱溶剂、重结晶、烘干得到化合物D8.3g,收率77.5%。HPLC:99.5%。1H NMR:δ1.37(12H,s),8.02-8.22(2H,8.08(dt,J=7.4,0.5Hz),8.16(dd,J=7.4,1.7Hz)),8.36(1H,dq,J=8.7,0.5Hz),8.57(1H,dd,J=8.7,1.9Hz),8.92-9.06(2H,8.97(dd,J=1.7,0.5Hz),9.01(dd,J=1.8,0.6Hz)),9.48(1H,dd,J=1.8,0.6Hz),9.60(1H,dt,J=1.9,0.5Hz).
元素分析结构:分子式为C21H20BN3O2;LC-MS检测产物分子量:357.16。
5、化合物E的制备方法:
以化合物C和芳基硼酸为主要原料,依次加入化合物C和芳基硼酸,碳酸钾、水,钯催化剂、用甲苯搅拌混合,碳酸钾水溶液提供碱性环境,控温70~80℃反应,保温12~24h,取样TLC检测,显示化合物C无剩余,经水洗,脱溶剂,过柱,甲苯精制得到最终产物;
或以化合物结构D和卤代芳烃为主要原料同样依次加入化合物D和卤代芳烃,碳酸钾,水,四(三苯基膦)钯,用甲苯搅拌混合,碳酸钾水溶液提供碱性环境,控温70~80℃反应,保温12~24h,取样TLC检测,显示化合物D无剩余,经水洗,脱溶剂,过柱,甲苯精制得到最终产物。
其中所述芳基硼酸为苯硼酸、2-联苯硼酸、2-三联苯硼酸、2-萘硼酸、1-芘硼酸、3-二苯并呋喃硼酸、9,9-二甲基-1-芴硼酸、N-苯基-2-咔唑硼酸、9,9-二苯基-2-芴硼酸等;卤代芳烃为氯苯,碘苯,溴苯,1-溴萘,2-碘萘,3-溴二苯并呋喃,9-溴菲,2-溴-9,9-二甲基芴,3-溴-N-苯基咔唑,4-氯联苯等。
实施例1:化合物1
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),苯硼酸13.7g(113mmol),碳酸钾38.7g(280mmol),水90ml,四(三苯基膦)钯1.3g(1.13mmol),使用甲苯300ml搅拌混合,升温至75~85℃保温反应,TLC跟踪反应,大约10h反应完全无化合物C剩余,然后静置分层,有机相经水洗、脱溶剂、硅胶柱层析、甲苯重结晶、烘干得到化合物1黄色固体26g,HPLC 99.9%,收率75%。
元素分析结构:分子式为C21H13N3;LC-MS检测产物分子量:307.11;1H NMR:δ7.46(1H,tdd,J=7.7,2.5,2.3Hz),7.66-7.91(4H,7.73(dddd,J=8.2,7.7,1.6,0.5Hz),7.84(dddd,J=8.2,2.6,2.4,0.5Hz)),7.94-8.17(2H,8.01(dt,J=8.7,0.5Hz),8.11(dq,J=8.7,0.5Hz)),8.25(1H,dd,J=1.5,0.5Hz),8.43-8.60(2H,8.49(dd,J=8.7,1.5Hz),8.54(dd,J=8.7,1.9Hz)),9.01(1H,dd,J=2.0,0.6Hz),9.48(1H,dd,J=2.0,0.5Hz),9.61(1H,dt,J=1.9,0.5Hz).
实施例2:化合物2
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),氘代苯硼酸14.3g(113mmol),碳酸钾38.7g(280mmol),水90ml,四(三苯基膦)钯1.3g(1.13mmol),使用甲苯300ml搅拌混合,升温至75~85℃保温反应,TLC跟踪反应,大约5h反应完全无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、硅胶柱层析、甲苯重结晶、烘干得到化合物2淡黄色固体25.5g,HPLC 99.89%,收率78%。
元素分析结构:分子式为C21H8D5N3;LC-MS检测产物分子量:312.07;1H NMR:7.84(dddd,J=8.2,2.6,2.4,0.5Hz)),7.94-8.17(2H,8.01(dt,J=8.7,0.5Hz),8.11(dq,J=8.7,0.5Hz)),8.25(1H,dd,J=1.5,0.5Hz),8.43-8.60(2H,8.49(dd,J=8.7,1.5Hz),8.54(dd,J=8.7,1.9Hz)),9.01(1H,dd,J=2.0,0.6Hz),9.48(1H,dd,J=2.0,0.5Hz),9.61(1H,dt,J=1.9,0.5Hz).
实施例3:化合物3
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),2-联苯硼酸22.3g(113mmol),碳酸钾38.7g(280mmol),水90ml,醋酸钯0.25g(1.13mmol),2-二环己基磷-2’,4’,6’-三异丙基联苯1.1g(2.26mmol)使用300ml甲苯搅拌混合,升温至65~75℃保温反应,TLC跟踪反应,大约6h反应完全无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物3黄色固体35.3g,HPLC99.91%,收率81.9%。
元素分析结构:分子式为C27H17N3;LC-MS检测产物分子量:383.14;1H NMR:δ7.45(1H,tdd,J=7.8,2.4,1.1Hz),7.57-7.87(7H,7.66(ddd,J=7.9,7.7,2.6Hz),7.67(dddd,J=8.4,1.8,1.5,0.5Hz),7.78(dddd,J=8.4,7.8,1.6,0.5Hz),7.78(ddd,J=8.0,7.7,2.2Hz),7.83(dt,J=8.7,0.5Hz)),8.18(1H,dq,J=8.7,0.5Hz),8.21-8.37(2H,8.27(dd,J=1.3,0.5Hz),8.3(ddd,J=8.0,2.6,0.5Hz)),8.43-8.61(3H,8.49(dd,J=8.7,1.3Hz),8.53(ddd,J=7.9,2.2,0.5Hz),8.58(dd,J=8.7,1.9Hz)),9.03(1H,dd,J=2.0,0.6Hz),9.4(1H,dd,J=2.0,0.5Hz),9.72(1H,dt,J=1.9,0.5Hz).
实施例4:化合物6
合成路线:
具体制备步骤如下:
化合物F使用已知方法(Voituriez,Arnaud;et al Advanced Synthesis&Catalysis(2006),348(16+17),2363-2370,碱与催化剂有所改变)的制备:
氮气保护下,于500ml三口瓶中依次加入间溴碘苯33.4g(118.1mmol),氘代苯硼酸15.0g(118.1mmol),碳酸钾40.7g(294.5mmol),水94.9ml,四(三苯基膦)钯1.36g(1.18mmol),使用330ml二氧六环搅拌混合,升温至100~105℃回流保温反应,TLC跟踪反应,大约6h反应无氘代苯硼酸剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物F,类白色固体25g,HPLC:99.5%,收率92%。元素分析结构:分子式为C12H4D5Br;LC-MS检测产物分子量:237.02。
化合物6的制备:
氮气保护下,于500ml三口瓶中依次加入化合物D 30g(83.9mmol),化合物F20.0g(83.9mmol),碳酸钾28.9g(209.9mmol),水67.6g,醋酸钯0.19g(0.84mmol),三环己基膦0.47g(1.68mmol)使用300g甲苯搅拌混合,升温至75~85℃保温反应,TLC跟踪反应,大约3h反应无化合物D剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物6白色固体30g,HPLC:99.89%,收率92%。
元素分析结构:分子式为C27H12D5N3;LC-MS检测产物分子量:388.17;1H NMR:δ7.51-7.81(4H,7.57(tdd,J=7.6,2.7,1.4Hz),7.62(dddd,J=7.8,7.6,1.6,0.5Hz),7.74(dt,J=8.6,2.6Hz)),7.82-8.10(6H,7.89(ddd,J=8.6,8.2,0.5Hz),7.91(dddd,J=7.8,2.0,1.9,0.5Hz),7.99(ddd,J=8.2,2.8,2.7Hz),8.04(dt,J=8.7,0.5Hz),8.04(dq,J=8.7,0.5Hz)),8.28(1H,dd,J=1.3,0.5Hz),8.43-8.75(3H,8.49(dd,J=8.7,1.3Hz),8.58(dd,J=8.7,1.7Hz),8.70(ddd,J=2.8,2.6,0.5Hz)),9.01(1H,dd,J=2.0,0.5Hz),9.41(1H,dd,J=2.0,0.5Hz),9.68(1H,dt,J=1.7,0.5Hz).
实施例5:化合物9
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),2-三联苯硼酸31g(113mmol),碳酸钾38.7g(280mmol),水90ml,四(三苯基膦)钯1.3g(1.13mmol),使用300ml甲苯搅拌混合,升温至70~78℃保温反应,TLC跟踪反应,10h反应无化合物C剩余,反应毕分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物9白色固体45g,HPLC99.94%,收率86.7%。
元素分析结构:分子式为C33H21N3;LC-MS检测产物分子量:459.17;1H NMR:δ7.46(1H,tdd,J=7.8,1.8,1.6Hz),7.64-7.95(8H,7.71(ddd,J=7.7,7.4,2.2Hz),7.71(dddd,J=8.4,1.7,1.5,0.5Hz),7.80(ddd,J=7.7,7.4,2.2Hz),7.84(dddd,J=8.4,7.8,1.6,0.5Hz),7.89(ddd,J=7.3,1.8,0.4Hz)),8.16-8.32(3H,8.22(dq,J=7.5,0.5Hz),8.23(dt,J=7.6,0.5Hz),8.27(dd,J=1.3,0.5Hz)),8.43-8.65(5H,8.49(dd,J=7.6,1.3Hz),8.49(ddd,J=7.4,2.2,0.5Hz),8.56(ddd,J=7.4,2.2,0.5Hz),8.59(ddd,J=7.3,2.0,0.4Hz)),8.74(1H,dd,J=7.5,1.8Hz),9.00(1H,dd,J=2.0,0.6Hz),9.40(1H,dd,J=2.0,0.5Hz),9.67(1H,dt,J=1.8,0.5Hz).
实施例6:化合物10
合成路线:
具体制备步骤如下:
化合物G使用已知方法(Lee,Sang Ho;et al Journal of the AmericanChemical Society(2005),127(25),9071-9078,碱与催化剂根据实际情况有所改变)制备:
氮气保护下,于500ml三口瓶中依次加入2-溴-4'-碘-1,1'-联苯42.4g(118.1mmol),氘代苯硼酸18.0g(141.7mmol),氢氧化钾16.5g(295.4mmol),水93.7ml,四(三苯基膦)钯1.36g(1.18mmol),使用400ml甲苯搅拌混合,升温至80~85℃回流保温反应,TLC跟踪反应,大约12h反应氘代苯硼酸无剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物G,白色固体35g,HPLC:99.48%,收率94%。元素分析结构:分子式为C18H8D5Br;LC-MS检测产物分子量:313.05;
化合物10的制备:
氮气保护下,于500ml三口瓶中依次加入化合物D 30g(83.9mmol),化合物G 26.3g(83.9mmol),碳酸钾28.9g(209mmol),水68ml,四(三苯基膦)钯0.97g(8.39mmol),使用300ml甲苯搅拌混合,升温至75~85℃保温反应,TLC跟踪反应,大约12h反应无化合物D剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物10白色固体36g,HPLC:99.95%,收率92.3%。
元素分析结构:分子式为C33H16D5N3;LC-MS检测产物分子量:464.20;1H NMR:7.64-7.95(4H,7.71(ddd,J=7.7,7.4,2.2Hz),7.71(dddd,J=8.4,1.7,1.5,0.5Hz),7.80(ddd,J=7.7,7.4,2.2Hz),7.84(dddd,J=8.4,7.8,1.6,0.5Hz),7.89(ddd,J=7.3,1.8,0.4Hz)),8.16-8.32(3H,8.22(dq,J=7.5,0.5Hz),8.23(dt,J=7.6,0.5Hz),8.27(dd,J=1.3,0.5Hz)),8.43-8.65(5H,8.49(dd,J=7.6,1.3Hz),8.49(ddd,J=7.4,2.2,0.5Hz),8.56(ddd,J=7.4,2.2,0.5Hz),8.59(ddd,J=7.3,2.0,0.4Hz)),8.74(1H,dd,J=7.5,1.8Hz),9.00(1H,dd,J=2.0,0.6Hz),9.40(1H,dd,J=2.0,0.5Hz),9.67(1H,dt,J=1.8,0.5Hz).
实施例7:化合物12
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),2-萘硼酸19.4g(113mmol),碳酸钾38.7g(280mmol),水90ml,三(二亚苄基丙酮)二钯1.03g(1.13mmol),三苯基膦0.59g(2.26mmol),使用300g甲苯搅拌混合,升温至85~90℃保温反应,TLC跟踪反应,大约10h反应无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物12白色固体36g,HPLC99.92%,收率89%。
元素分析结构:分子式为C25H15N3;LC-MS检测产物分子量:357.13;1H NMR:δ7.67-7.89(4H,7.74(dddd,J=7.7,7.2,2.6,0.4Hz),7.77(dddd,J=8.2,7.7,1.9,0.4Hz),7.81(dt,J=8.7,0.5Hz),7.83(ddd,J=8.5,2.0,0.4Hz)),8.07-8.33(3H,8.13(dq,J=8.7,0.5Hz),8.18(dddt,J=8.2,2.6,2.2,0.5Hz),8.28(dd,J=1.3,0.5Hz)),8.40-8.64(4H,8.46(dd,J=8.7,1.7Hz),8.49(dd,J=8.7,1.3Hz),8.49(dddq,J=7.2,2.0,1.9,0.5Hz),8.57(dddt,J=8.5,2.0,0.5,0.4Hz)),8.79(1H,ddtd,J=2.2,2.0,0.5,0.4Hz),9.01(1H,dd,J=1.8,0.5Hz),9.42(1H,dd,J=1.8,0.5Hz),9.68(1H,dt,J=1.7,0.5Hz).
实施例8:化合物16
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),1-芘硼酸27.8g(113mmol),碳酸钾38.7g(280mmol),水90ml,三(二亚苄基丙酮)二钯1.03g(1.13mmol),三苯基膦0.59g(2.26mmol),使用300ml甲苯搅拌混合,升温至85~95℃保温反应,TLC跟踪反应,大约3h反应无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到产物白色固体43g,HPLC99.90%,收率88%。
元素分析结构:分子式为C31H17N3;LC-MS检测产物分子量:431.14;1H NMR:δ7.85(1H,ddd,J=7.2,5.9,0.4Hz),8.04(1H,ddt,J=6.0,5.8,0.4Hz),8.18-8.39(2H,8.24(dt,J=7.5,0.5Hz),8.33(dtd,J=6.0,2.0,0.5Hz)),8.40-8.67(7H,8.46(dt,J=5.8,2.0Hz),8.49(dd,J=7.5,1.3Hz),8.53(dq,J=6.1,0.5Hz),8.55(dd,J=1.3,0.5Hz),8.59(ddd,J=7.2,2.0,0.5Hz),8.60(dddd,J=5.1,2.0,0.5,0.4Hz),8.61(dddd,J=5.9,2.0,1.8,0.5Hz)),8.71-8.86(2H,8.77(dd,J=6.1,1.8Hz),8.80(dddd,J=5.1,1.8,0.5,0.4Hz)),9.01(1H,dd,J=2.0,0.5Hz),9.14(1H,dt,J=2.0,0.5Hz),9.50(1H,dd,J=2.0,0.5Hz),9.67(1H,dt,J=1.8,0.5Hz).
实施例9:化合物32
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),3-二苯并呋喃硼酸24g(113mmol),碳酸钾38.7g(280mmol),水90ml,醋酸钯0.25g(1.13mmol),三环己基膦0.63(2.26mmol),使用300ml甲苯搅拌混合,使用油浴锅升温至75~85℃保温反应,TLC跟踪反应,大约5h反应完全,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物32白色固体40g,HPLC 99.94%,收率88.9%。
元素分析结构:分子式为C27H15N3O;LC-MS检测产物分子量:397.43;1H NMR:δ7.92-8.18(4H,7.98(dd,J=7.8,2.0Hz),8.08(dd,J=2.0,0.5Hz),8.10(ddd,J=5.5,5.0,1.5Hz),8.12(ddd,J=5.5,1.5,0.5Hz)),8.61-9.07(8H,8.67(td,J=5.0,1.5Hz),8.73(dq,J=6.2,0.5Hz),8.74(ddt,J=5.0,1.5,0.5Hz),8.80(dd,J=6.2,1.7Hz),8.85(dt,J=7.8,0.5Hz),8.88(dd,J=6.2,1.7Hz),8.98(dd,J=1.7,0.5Hz),9.02(dd,J=2.0,0.5Hz)),9.24(1H,dt,J=6.2,0.5Hz),9.39(1H,dd,J=2.0,0.5Hz),9.62(1H,dt,J=1.7,0.5Hz).
实施例10:化合物41
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),9,9-二甲基-1-芴硼酸26.9g(113mmol),碳酸钾38.7g(280mmol),水90ml,三(二亚苄基丙酮)二钯1.03g(1.13mmol),三苯基膦0.59g(2.26mmol),使用300ml甲苯搅拌混合,升温至70~85℃保温反应,TLC跟踪反应,大约12h反应无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物41白色固体40g,HPLC:99.94%,收率83.7%。
元素分析结构:分子式为C30H21N3;LC-MS检测产物分子量:424.17;1H NMR:δ2.31(6H,s),7.45-8.06(9H,7.52(ddd,J=8.2,7.8,2.5Hz),7.63(ddd,J=8.3,7.8,1.6Hz),7.65(dd,J=8.6,2.8Hz),7.69(dd,J=7.5,2.8Hz),7.71(dt,J=8.7,0.5Hz),7.77(dd,J=8.6,7.5Hz),7.79(ddd,J=8.2,1.6,0.4Hz),7.88(ddd,J=8.3,2.5,0.4Hz),8.00(dq,J=8.7,0.5Hz)),8.37(1H,dd,J=8.7,1.4Hz),8.52-8.64(2H,8.58(dd,J=8.7,1.8Hz),8.58(dd,J=1.4,0.5Hz)),8.98(1H,dd,J=2.0,0.5Hz),9.39(1H,dd,J=2.0,0.5Hz),9.66(1H,dt,J=1.8,0.5Hz).
实施例11:化合物44
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),N-苯基-2-咔唑硼酸32.4g(113mmol),碳酸钾38.7g(280mmol),水90ml,醋酸钯0.25g(1.13mmol),三环己基膦0.63(2.26mmol),使用300ml甲苯搅拌混合,使用油浴锅升温至85~90℃保温反应,TLC跟踪反应,大约3h反应完全,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物44白色固体47g,HPLC:99.95%,收率88%。
元素分析结构:分子式为C33H20N4;LC-MS检测产物分子量:472.17;1H NMR:δ7.44(1H,tdd,J=7.6,1.7,1.0Hz),7.58(2H,dddd,J=8.1,7.6,1.5,0.4Hz),7.91(2H,dtd,J=8.1,1.3,0.4Hz),8.09-8.25(2H,8.14(td,J=5.0,1.7Hz),8.19(dd,J=5.1,2.0Hz)),8.29-8.50(2H,8.34(dd,J=2.0,0.5Hz),8.45(td,J=5.0,1.8Hz)),8.69-9.15(7H,8.75(dq,J=6.2,0.5Hz),8.78(dd,J=6.1,1.7Hz),8.87(dd,J=1.9,0.5Hz),8.88(dd,J=6.2,1.7Hz),8.90(ddd,J=5.0,1.7,0.5Hz),9.01(ddt,J=5.0,1.8,0.5Hz),9.09(dt,J=5.1,0.5Hz)),9.18-9.43(3H,9.23(dt,J=6.1,0.5Hz),9.33(dd,J=1.7,0.5Hz),9.38(dd,J=1.9,0.5Hz)),9.53(1H,dt,J=1.7,0.5Hz).
实施例12:化合物46
合成路线:
具体制备步骤如下:
化合物H使用已知方法(Suzuki,Ken;et al Advanced Synthesis&Catalysis(2008),350(5),652-656,碱与催化剂根据实际情况有所改变)制备:
氮气保护下,于500ml三口瓶中依次加入2-氯-9H-咔唑24.9g(123.4mmol),氘代溴苯22g(135.7mmol),叔丁醇钠14.2g(148.1mmol),三(二亚苄基丙酮)二钯1.12g(1.23mmol),2-二环己基磷-2’,4’,6’-三异丙基联苯1.17g(2.26mmol)使用250ml甲苯搅拌混合,升温至100~105℃保温反应,TLC跟踪反应,大约3h反应无2-氯-9H-咔唑剩余,反应毕向体系中加入100g水水解,分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物H,黄色固体32g,HPLC:98.98%,收率91.5%。元素分析结构:分子式为C18H7D5ClN;LC-MS检测产物分子量:282.10;
化合物48的制备:
氮气保护下,于500ml三口瓶中依次加入化合物D 30g(83.9mmol),化合物H23.7g(83.9mmol),碳酸钾28.9g(209.75mmol),水70ml,三(二亚苄基丙酮)二钯0.77g(0.84mmol),三苯基膦0.44g(1.68mmol),使用300ml甲苯搅拌混合,升温至60~70℃保温反应,TLC跟踪反应,大约5h反应至无化合物D剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物46黄色固体35g,HPLC:99.78%,收率87.5%。
元素分析结构:分子式为C33H15D5N4;LC-MS检测产物分子量:477.20;1H NMR:8.09-8.25(2H,8.14(td,J=5.0,1.7Hz),8.19(dd,J=5.1,2.0Hz)),8.29-8.50(2H,8.34(dd,J=2.0,0.5Hz),8.45(td,J=5.0,1.8Hz)),8.72-9.44(10H,8.78(dd,J=6.1,1.7Hz),8.87(dd,J=6.1,1.7Hz),8.88(dd,J=1.9,0.5Hz),8.90(ddd,J=5.0,1.7,0.5Hz),9.01(ddt,J=5.0,1.8,0.5Hz),9.09(dt,J=5.1,0.5Hz),9.21(dq,J=6.1,0.5Hz),9.23(dt,J=6.1,0.5Hz),9.33(dd,J=1.7,0.5Hz),9.38(dd,J=1.9,0.5Hz)),9.53(1H,dt,J=1.7,0.5Hz).
实施例13:化合物50
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物C 30g(113mmol),9,9-二苯基-2-芴硼酸40.9g(113mmol),碳酸钾38.7g(280mmol),水90ml,醋酸钯0.25g(1.13mmol),2-二环己基磷-2’,4’,6’-三异丙基联苯1.08g(2.26mmol),使用300ml甲苯搅拌混合,升温至85~95℃保温反应,TLC跟踪反应,大约24h反应至无化合物C剩余,反应毕体系分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物50灰褐色固体50g,HPLC:99.95%,收率80.8%。
元素分析结构:分子式为C40H25N3;LC-MS检测产物分子量:547.20;1H NMR:δ7.16-7.34(10H,7.22(dddd,J=8.0,1.3,1.1,0.6Hz),7.23(tt,J=7.7,1.1Hz),7.27(dddd,J=8.0,7.7,1.8,0.6Hz)),7.49-7.85(6H,7.57(ddd,J=8.4,8.1,1.8Hz),7.63(ddd,J=8.3,1.8,0.5Hz),7.66(ddd,J=8.3,8.1,1.8Hz),7.72(dd,J=7.9,1.9Hz),7.78(dt,J=7.9,0.5Hz),7.79(ddd,J=8.4,1.8,0.5Hz)),8.05-8.30(3H,8.11(dq,J=8.7,0.5Hz),8.18(dd,J=1.9,0.4Hz),8.25(dd,J=1.3,0.5Hz)),8.35-8.59(3H,8.41(dd,J=7.9,0.4Hz),8.49(dd,J=7.9,1.3Hz),8.53(dd,J=8.7,1.9Hz)),8.98(1H,dd,J=2.0,0.6Hz),9.38(1H,dd,J=2.0,0.5Hz),9.66(1H,dt,J=1.9,0.5Hz).
实施例14:化合物52
合成路线:
具体制备步骤如下:
氮气保护下,于500ml三口瓶中依次加入化合物D 30g(84mmol),2-氯-4,6-二苯基-1,3,5-三嗪22.48g(84mmol),碳酸钾29.0g(210mmol),水70ml,甲苯300ml,三(二亚苄基丙酮)二钯0.77g(0.84mmol),2-二环己基磷-2’,4’,6’-三异丙基联苯0.76g(1.6mmol),搅拌升温至65~75℃保温反应,TLC跟踪反应,8h反应至无化合物D剩余,分层,有机相经水洗、脱溶剂、甲苯重结晶、烘干得到化合物52固体28g,HPLC:99.90%,收率72.1%。
元素分析结构:分子式为C30H18N6;LC-MS检测产物分子量:462.16;1H NMR:δ7.73-8.03(7H,7.80(dddd,J=8.2,7.6,2.3,0.5Hz),7.91(dt,J=8.7,0.5Hz),7.97(tt,J=7.6,1.5Hz)),8.12-8.33(5H,8.18(dq,J=7.6,0.5Hz),8.26(dtd,J=8.2,1.6,0.5Hz)),8.53-8.74(2H,8.59(dd,J=8.7,1.3Hz),8.68(dd,J=1.3,0.5Hz)),8.80(1H,dd,J=7.6,1.7Hz),9.04(1H,dd,J=1.7,0.6Hz),9.51(1H,dd,J=1.7,0.5Hz),9.67(1H,dt,J=1.7,0.5Hz).
应用例1:
本应用例提供一种有机电致发光器件,结构示意图如图1所示。其中,使用的基底1是涂覆厚度为30nm的结构化ITO 2(氧化铟锡)的玻璃板。依次利用丙酮和异丙醇对ITO 2(氧化铟锡)玻璃板进行超声波洗涤,并且接着储存在异丙醇中。接着将ITO衬底安装在真空气相沉积设备的衬底固持器上。将化合物HIM-1引入到所述真空气相沉积设备的单元中,并且接着将所述设备的腔室中的压力控制为10E-6托。使用如下所示的结构的化合物:
此后,将电流施加到所述单元以蒸发上述引入的材料,由此在ITO 2衬底上形成厚度为70nm的空穴注入层3。接着将化合物HTL-1引入到所述真空气相沉积设备的另一个单元中,并且通过向所述单元施加电流来蒸发,由此在空穴注入层3上形成厚度是40nm的空穴传输层4。此后,将本发明的化合物引入到真空气相沉积设备的一个单元中作为主体材料,并且掺杂剂G引入到另一个单元中。以不同速率蒸发两种材料,以使得掺杂剂以按主体和掺杂剂的总量计20重量%的掺杂量沉积,在空穴传输层4上形成厚度为50nm的发光层5。
接着将化合物ETM-1引入到一个单元中,并且将化合物ETM-2引入到另一个单元中。所述两种材料以相同比率蒸发。使得其分别以50重量%的掺杂量沉积以在发光层5上形成厚度为20nm的电子传输层6。在电子传输层6上沉积ETM-2形成厚度为20nm的电子注入层7。阴极反射电极层8由厚度100nm的铝层的蒸镀形成。最终形成有机电致发光元件。
采能用应用例1相同的方法进行应用例2-14和对比例1-3,不同之处在于各个应用例和对比例中的发光层主体材料不同,应用例1-14和对比例1-3中有机电致发光器件中使用的材料为表1所示。
对于通过上述方式制作的有机电致发光元件测定电致发光光谱、呈现朗伯发射特性的电流-电压-发光密度特性(IUL特性)和(工作)寿命。所述IUL特性用于确定参数如工作电压U(以V为单位)和特定亮度下的外量子效率(以%为单位)。在10000cd/m2下的LD80是在给定起始亮度10000cd/m2下,OLED已经降至起始强度的80%,即降至8000cd/m2时的寿命。各种OLED的光电子特性整理在表2中。
表1
表2
本发明的化合物作为发光层主体材料,由表2可知,使用了本发明的化合物的有机电致发光元件,相对于现有技术,特别在寿命以及效率和工作电压方面产生改进。可以由低电压驱动且显示出高的发光效率。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
4.一种根据权利要求1-3任意一项所述高性能光电材料的制备方法,其特征在于,所述的制备方法为:
S1、化合物A的制备:
在有机溶剂中加入6-溴喹唑啉,在一定温度下,滴加正丁基锂正己烷溶液,然后控制反应温度,滴加DMF,反应毕,经后处理得到化合物A;
S2、化合物B的制备:
在有机溶剂中,化合物A、2-溴-4-氯-苯胺和对甲苯磺酸混合后,加热反应,反应毕,经过后处理得到化合物B;
S3、化合物C的制备:
在惰性气体保护下,化合物B、碳酸铯、THF、醋酸钯和三环己基膦混合后,升温回流反应,反应毕,经后处理得到化合物C;
S4、化合物D的制备:
在惰性气体保护下,化合物C、联硼酸频哪醇酯、乙酸钾、Pd(dba)2、三环己基膦、二氧六环混合,加热反应,反应毕,经后处理得到化合物D;
S5、化合物E的制备:
以化合物C和芳基硼酸为主要原料,化合物C和芳基硼酸,碳酸钾、水,钯催化剂加入到有机溶剂中,碳酸钾水溶液提供碱性环境,控温反应温度进行反应,反应毕,经后处理得到化合物E;
或者,以化合物D和卤代芳烃为主要原料,化合物D和卤代芳烃,碳酸钾,水,四(三苯基膦)钯,加入到有机溶剂中,碳酸钾水溶液提供碱性环境,控温反应温度进行反应,反应毕,经后处理得到化合物E;
所述的X为Cl、Br或I。
5.根据权利要求4所述高性能光电材料的制备方法,其特征在于,步骤S5中,所述芳基硼酸为苯硼酸、2-联苯硼酸、2-三联苯硼酸、2-萘硼酸、1-芘硼酸、3-二苯并呋喃硼酸、9,9-二甲基-1-芴硼酸、N-苯基-2-咔唑硼酸、9,9-二苯基-2-芴硼酸。
6.根据权利要求4所述高性能光电材料的制备方法,其特征在于,步骤S5中,所述卤代芳烃为氯苯,碘苯,溴苯,1-溴萘,2-碘萘,3-溴二苯并呋喃,9-溴菲,2-溴-9,9-二甲基芴,3-溴-N-苯基咔唑,4-氯联。
7.根据权利要求4所述高性能光电材料的制备方法,其特征在于,步骤S5中,以化合物C和芳基硼酸为主要原料时,反应温度为70~80℃,反应时间为12~24h,有机溶剂为甲苯;
以化合物D和卤代芳烃为主要原料时,反应温度为70~80℃,反应时间为12~24h,有机溶剂为甲苯。
8.一种有机电致发光器件,其特征在于,所述的有机电致发光器件中含有权利要求1-3任意一项所述光电材料的一种或至少两种组合。
9.根据权利要求8所述的一种有机电致发光器件,其特征在于,所述有机电致发光器件包括阳极、阴极以及夹在阳极与阴极之间的有机薄膜层,所述的有机薄膜层包括发光层。
10.根据权利要求9所述的一种有机电致发光器件,其特征在于,所述发光层中含有权利要求1-3中任意一项所述光电材料的一种或至少两种组合。
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