CN108586483A - 一种以s,s-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物及其制备方法 - Google Patents
一种以s,s-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种以S,S‑二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物及其制备方法；在惰性气氛中，将2‑(三甲基锡)‑5‑(4‑正己基苯基)噻吩(1)，3,7‑二溴‑S,S‑二氧‑二苯并噻吩(2)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到3‑溴‑7‑(5‑己基‑2,2’‑二噻吩基)二苯并噻吩‑S,S‑二氧化物；将3‑溴‑7‑(5‑己基‑2,2’‑二噻吩基)二苯并噻吩‑S,S‑二氧化物，中间体2,6‑二(三甲基锡)‑4,8‑二(2‑乙基己氧基)苯并[1,2‑b:4,5‑b’]二噻吩(3)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到齐聚噻吩衍生物有机半导体材料；其具有较低的HOMO能级和合适的光学带隙，应用于有机发光二极管和有机太阳能电池器件制备的新材料。
Description
技术领域
本实发明涉及噻吩衍生物及有机半导体材料领域，尤其涉及一种以S,S- 二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物及其制备方法。
背景技术
齐聚噻吩及其衍生物具有优异的光电转换效率，良好的环境稳定性,适宜的能级以及良好的可修饰性，近年来常被运用于有机发光二极管(OLED)、有机场效应管(OFET)、有机太阳能电池(OSV)等领域。
在半导体材料分子结构中构筑给电子单元-受电子单元(D-A)交替结构，可有效提高载流子的迁移率，从而获得良好的半导体性能。二苯并噻吩是一种常见的噻吩衍生物，常被引入有机半导体材料分子结构中作为给电子单元，若将其噻吩环上的硫原子氧化，即可转变为新的受电子单元：二苯并噻吩 -S,S-二氧化物(DBTSO)。DBTSO单元具有较高的亲和势，有利于电子的注入和传输。其不仅具有荧光量子产率高、热稳定性好等特点，同时因其硫原子处于最高的化学价态，使其同时具备了良好的抗氧化性能。近年来，研究者们把DBTSO受体单元与芴、咔唑、芳胺、喹喔啉或吡嗪等给电子单元键联，制备得到了一系列D-A型有机半导体新材料，并在OLED中展示出优异的器件性能。因此DBTSO是一种理想的半导体材料受电子单元。
发明内容
本发明的目的在于提供一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物及其制备方法，以解决上述技术问题。
为实现上述目的本发明采用以下技术方案：
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物，如下化学结构式P1所示：
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，包括如下步骤：
1)、在惰性气氛中，将2-(三甲基锡)-5-(4-正己基苯基)噻吩(1)，3,7-二溴 -S,S-二氧-二苯并噻吩(2)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)；
2)、在惰性气氛中，将3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)，中间体2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并[1,2-b:4,5-b’] 二噻吩(3)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到所述以S,S- 二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物有机半导体材料(P1)；
作为本发明进一步的方案，所述Stille交叉偶联反应的温度为100-120℃，反应时间为12-72小时。
作为本发明进一步的方案，3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)与中间体2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并 [1,2-b:4,5-b’]二噻吩(3)摩尔比为2:1。
作为本发明进一步的方案，3,7-二溴-S,S-二氧-二苯并噻吩(2)与2-(三甲基锡)-5-(4-正己基苯基)噻吩(1)摩尔比为3:1。
作为本发明进一步的方案，所述Stille交叉偶联反应在氮气氛围下进行。
作为本发明进一步的方案，所述Stille交叉偶联反应所用催化剂为四(三苯基膦)钯。
作为本发明进一步的方案，所述Stille交叉偶联反应所用溶剂为无水N,N- 二甲基甲酰胺(DMF)。
作为本发明进一步的方案，还包括以下步骤，反应所得中间产物和终产物的粗产物需进行萃取，干燥之后蒸发溶剂，再进行柱层析纯化。
作为本发明进一步的方案，萃取所用溶剂为二氯甲烷，柱层析所用洗脱剂为石油醚和二氯甲烷，体积比为1:2。
与现有技术相比，本发明具有以下优点：本发明涉及的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物，具有以下性能：1)合适的光学带隙，Eg opt(eV)＝-2.24eV。2)较低的HOMO能级。其HOMO能级为-5.35eV，LOMO能级为-2.86eV，电化学能隙(Eg ec)为-2.49eV，与UV-vis计算的光学带隙(-2.24eV)比较接近。3)相比在二氯甲烷溶液中，该噻吩衍生齐聚物在固体薄膜中的紫外吸收光谱和光致发光光谱均发生了一定波长的红移，分别为9nm和97nm。因此，以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物是一种有望应用于有机发光二极管(OLED)和有机太阳能电池 (OSC)器件制备的新材料。
附图说明
图1为一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的紫外吸收(UV-vis)光谱。
图2为一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的光致发光(PL)光谱。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细阐述。
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的具体合成流程如下所示：
实施例1
3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物的合成(M1)：
在500ml三口烧瓶中，将2-(三甲基锡)-5-(4-正己基苯基)噻吩(3.23g，7.37mmol)、3,7-二溴-S,S-二氧-二苯并噻吩(8.27g，22.10mmol)和四(三苯基膦) 钯(0.17g，0.15mmol)，溶于100ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下100℃搅拌反应48h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到褐色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到黄色固体M1，1.07g，产率27％。
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的合成(P1)：
在250ml三口烧瓶中，将2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并 [1,2-b:4,5-b’]二噻吩(0.77g，1.0mmol)、3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(1.07g，2mmol)和四(三苯基膦)钯(0.034g，0.03 mmol)，溶于110ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下110 ℃搅拌反应72h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到棕色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到褐色固体P1， 0.32g，产率23.5％。
实施例2
3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物的合成(M1)：
在500ml三口烧瓶中，将2-(三甲基锡)-5-(4-正己基苯基)噻吩(4.5g，10.3mmol)、3,7-二溴-S,S-二氧-二苯并噻吩(11.57g，30.9mmol)和四(三苯基膦) 钯(0.24g，0.21mmol)，溶于120ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下120℃搅拌反应36h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到褐色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到黄色固体M1，1.32g，产率24％。
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的合成 (P1)：
在250ml三口烧瓶中，将2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并 [1,2-b:4,5-b’]二噻吩(0.48g，0.6mmol)、3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(0.65g，1.2mmol)和四(三苯基膦)钯(0.023g，0.02 mmol)，溶于100ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下120 ℃搅拌反应60h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到棕色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到褐色固体P1， 0.23g，产率28.2％。
实施例3
3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物的合成(M1)：
在500ml三口烧瓶中，将2-(三甲基锡)-5-(4-正己基苯基)噻吩(7.4g，18.2mmol)、3,7-二溴-S,S-二氧-二苯并噻吩(20.42g，54.6mmol)和四(三苯基膦) 钯(0.7g，0.61mmol)，溶于160ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下120℃搅拌反应48h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到褐色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到黄色固体M1，2.74g，产率28％。
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的合成 (P1)：
在500ml三口烧瓶中，将2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并 [1,2-b:4,5-b’]二噻吩(1.3g，1.7mmol)、3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(1.83g，3.4mmol)和四(三苯基膦)钯(0.065g，0.57 mmol)，溶于130ml干燥的N,N-二甲基甲酰胺(DMF)中，氮气保护下120 ℃搅拌反应72h。反应结束后冷却至室温，加入蒸馏水，用二氯甲烷萃取三次，合并有机相，再用无水硫酸镁干燥，过滤，减压蒸馏，得到棕色粗产物。粗产物以二氯甲烷：石油醚(体积比1：2)为洗脱剂柱层析，得到褐色固体P1， 0.6g，产率26.0％。
一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的结构表征数据：
1H NMR(CDCl3,400Hz,δ/ppm):8.38(d,J＝11.2Hz,2H),8.25(t,J＝8.4 Hz,2H),8.07(dd,J＝8.4Hz,3.6Hz,4H),7.87(m,4H),7.73(m,4H),7.67(s,2H), 7.55(m,4H),7.46(d,J＝8.4Hz,4H),4.10(d,J＝6.4Hz,4H),2.68(d,J＝5.2Hz, 4H),1.67～1.26(m,34H),0.99～0.83(m,18H)。
本发明具有以下性能，合适的光学带隙，Egopt(eV)＝-2.24eV。较低的HOMO能级。其HOMO能级为-5.35eV，LOMO能级为-2.86eV，电化学能隙(Egec)为-2.49eV，与UV-vis计算的光学带隙(-2.24eV)比较接近。相比在二氯甲烷溶液中，该噻吩衍生齐聚物在固体薄膜中的紫外吸收光谱和光致发光光谱均发生了一定波长的红移，分别为9nm和97nm(如图1、2所示)。因此，以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物是一种有望应用于有机发光二极管(OLED)和有机太阳能电池(OSC)器件制备的新材料。
以上所述为本发明较佳实施例，对于本领域的普通技术人员而言，根据本发明的教导，在不脱离本发明的原理与精神的情况下，对实施方式所进行的改变、修改、替换和变型仍落入本发明的保护范围之内。
Claims (10)
1.一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物，其
特征在于，如下化学结构式P1所示：
2.一种如权利要求1所述的以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，包括如下步骤：
1)、在惰性气氛中，将2-(三甲基锡)-5-(4-正己基苯基)噻吩(1)，3,7-二溴-S,S-二氧-二苯并噻吩(2)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)；
2)、在惰性气氛中，将3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)，中间体2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并[1,2-b:4,5-b’]二噻吩(3)和催化剂溶于溶剂，进行Stille交叉偶联反应，得到所述以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物有机半导体材料(P1)；
3.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，所述Stille交叉偶联反应的温度为100-120℃，反应时间为12-72小时。
4.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，3-溴-7-(5-己基-2,2’-二噻吩基)二苯并噻吩-S,S-二氧化物(M1)与中间体2,6-二(三甲基锡)-4,8-二(2-乙基己氧基)苯并[1,2-b:4,5-b’]二噻吩(3)摩尔比为2:1。
5.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，3,7-二溴-S,S-二氧-二苯并噻吩(2)与2-(三甲基锡)-5-(4-正己基苯基)噻吩(1)摩尔比为3:1。
6.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，所述Stille交叉偶联反应在氮气氛围下进行。
7.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，所述Stille交叉偶联反应所用催化剂为四(三苯基膦)钯。
8.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，所述Stille交叉偶联反应所用溶剂为无水N,N-二甲基甲酰胺(DMF)。
9.根据权利要求2所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，还包括以下步骤，反应所得中间产物和终产物的粗产物需进行萃取，干燥之后蒸发溶剂，再进行柱层析纯化。
10.根据权利要求9所述的一种以S,S-二氧二苯并噻吩为受电子单元的齐聚噻吩衍生物的制备方法，其特征在于，萃取所用溶剂为二氯甲烷，柱层析所用洗脱剂为石油醚和二氯甲烷，体积比为1:2。
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| CN110105375A (zh) * | 2019-05-30 | 2019-08-09 | 西安理工大学 | 以二噻吩并吡咯为分子中心的给-受-给-受-给型齐聚噻吩衍生物及其制备方法 |
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| CN110105375A (zh) * | 2019-05-30 | 2019-08-09 | 西安理工大学 | 以二噻吩并吡咯为分子中心的给-受-给-受-给型齐聚噻吩衍生物及其制备方法 |
| CN110105375B (zh) * | 2019-05-30 | 2021-11-16 | 西安理工大学 | 以二噻吩并吡咯为分子中心的给-受-给-受-给型齐聚噻吩衍生物及其制备方法 |
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