CN113501939A - 吡啶并三氮唑类新型受体及其发光聚合物的合成与应用 - Google Patents
吡啶并三氮唑类新型受体及其发光聚合物的合成与应用 Download PDFInfo
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- CN113501939A CN113501939A CN202110986669.2A CN202110986669A CN113501939A CN 113501939 A CN113501939 A CN 113501939A CN 202110986669 A CN202110986669 A CN 202110986669A CN 113501939 A CN113501939 A CN 113501939A
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Abstract
本发明涉及一种吡啶并三氮唑类新型受体及其发光聚合物的合成与应用。所述发光聚合物其结构式如式I所示。以本发明吡啶并三氮唑类发光聚合物为半导体层制备的有机场效应晶体管有较高的空穴迁移率(最高为0.28cm2V‑1s‑1)和固态发光量子产率(最高为10％)，在有机场效应晶体管及发光晶体管中均具有良好的应用前景。本发明合成了一种吡啶并三氮唑(简称PT)类新型受体及其发光聚合物，并研究了其发光特性及在OFETs中的应用。本发明的吡啶并三氮唑类聚合物进一步扩展了发光聚合物材料的种类，在有机光电子器件中具有良好的应用前景。
Description
技术领域
本发明涉及一种吡啶并三氮唑类新型受体及其发光聚合物的合成与应用，属于材料领域。
背景技术
有机发光晶体管(OLETs)可能是目前最小的集成光电子装置，它同时结合了有机场效应晶体管(OFETs)的开关功能和有机发光二极管(OLEDs)的电发光特性。OLETs为研究有机半导体的电荷注入、电荷传输、电荷载体重组和光发射提供了良好的架构平台，这种独特的架构使其成为开发下一代显示技术和小型光子设备和电路的理想之选，有望应用于新型柔性显示器、有机电泵浦激光器和光通信技术等。
随着对有机光电子器件(如OFETs、有机光伏器件以及OLEDs等)逐步深入的研究，有机半导体的载流子迁移率和光电转换效率等方面已经取得了长足进步，然而同时具备高迁移率和发光特性的有机半导体材料的合成与制备一直以来都是一项巨大的挑战。
发明内容
本发明的目的是提供一种吡啶并三氮唑(PT)类新型受体及其发光聚合物的合成与应用，本发明研究了所制备的吡啶并三氮唑类聚合物的发光特性及OFETs性能，结果表明该类聚合物是一类具有高迁移率的发光半导体材料。
本发明所提供的吡啶并三氮唑类发光聚合物的结构式如式I所示：
式I中，R为碳原子总数为1～60的直链或支链烷基，n为5～100之间的自然数；
Donor选自如下A类基团中的任意一种：
所述A类基团中，
表示取代的位置。
本发明首先提供式1所示化合物：
式1中，R的定义同式I；具体可为5-癸基十五烷基。
式1所示化合物可按照如下步骤制备：
(1)在醋酸的水溶液中，式2所示2,5-二溴-3,4-二氨基吡啶与亚硝酸钠进行反应得到式3所示4,7-二溴-2H-[1,2,3]三氮唑并[4,5-c]吡啶；
(2)在碳酸钾存在的条件下，式3所示4,7-二溴-2H-[1,2,3]三氮唑并[4,5-c]吡啶与R-I所示碘代烷反应得到式4所示4,7-二溴-2-烷基-2H-[1,2,3]三氮唑并[4,5-c]吡啶；R-I中R的定义同式I；
式4中，R的定义同式I；
(3)在催化剂存在下，式4所示4,7-二溴-2-烷基-2H-[1,2,3]三氮唑并[4,5-c]吡啶与2,5-双(三甲基锡)噻吩并[3,2-b]噻吩发生偶联反应，得到式1所示化合物；
上述方法步骤(1)中，所述醋酸的水溶液中，水和醋酸体积比可为1：0.5～5.0，具体可为1：2.5；
式2所示2,5-二溴-3,4-二氨基吡啶与亚硝酸钠的摩尔比可为1：0.5～4.0，具体可为1：1.5；
所述反应的温度可为10～40℃，具体可为30℃，时间可为2～60小时，具体可为24h。
上述方法步骤(2)中，式3所示4,7-二溴-2H-[1,2,3]三唑并[4,5-c]吡啶、碘代烷与所述碳酸钾的摩尔比依次可为1：1.0～2.0：1.0～4.0，具体可为1：1.2：2.0；
所述反应的温度可为80～120℃，具体可为90℃，时间可为2～48小时，具体可为24h；
所述反应在有机溶剂中进行，所述有机溶剂具体可为N,N-二甲基甲酰胺；
上述方法步骤(3)中，所述催化剂可为四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中至少一种，具体可为二(三苯基膦)二氯化钯；
式4所示4,7-二溴-2-烷基-2H-[1,2,3]三氮唑并[4,5-c]吡啶与2,5-双(三甲基锡)噻吩并[3,2-b]噻吩的摩尔比可为2：0.95～1.05，具体可为2：1；
式4所示化合物与所述催化剂的摩尔比可为1：0.01～0.10，具体可为1：0.025；
上述制备方法中，所述偶联反应的温度可为90～140℃，具体可为120℃，时间可为2小时～80小时，具体可为24小时；
所述反应在如下溶剂中进行：甲苯、氯苯和二甲苯中至少一种。
本发明所提供的吡啶并三氮唑类发光聚合物具体可为聚合物PPT-TT-PT-2FBT和PPT-TT-PT-TT；
所述聚合物PPT-TT-PT-2FBT具体如式I-1所示，其中，n＝20：
其中R的定义与前述式I中R的定义相同。
所述聚合物PPT-TT-PT-TT具体如式I-2所示，其中，n＝16:
其中R的定义与前述式I中R的定义相同。
本发明进一步提供了所述吡啶并三氮唑类发光聚合物的制备方法，包括如下步骤：
在催化剂和配体存在的条件下，式1所示化合物与Me3Sn-Donor-SnMe3双甲基锡试剂经聚合反应即得所述吡啶并三氮唑类发光聚合物：
R的定义与前述式I中R的定义相同。
其中，双甲基锡化合物选自如下化合物中的任意一种：
上述的制备方法中，所述催化剂可为四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中至少一种；
所述配体可为三苯基膦、三(邻甲苯基)膦和三苯基砷中至少一种。
上述的制备方法中，式1所示化合物与所述双甲基锡试剂的摩尔比可为1：0.95～1.05，具体可为1：1；
式1所示化合物与所述催化剂的摩尔比可为1：0.01～0.10，具体可为1：0.03；
式1所示化合物与所述配体的摩尔比可为1：0.08～0.80，具体可为1：0.24。
上述的制备方法中，所述聚合反应的温度可为90～140℃，具体可为120℃或125℃，时间可为2小时～80小时，具体可为24小时或48h；
所述聚合反应在如下溶剂中进行：甲苯、氯苯和二甲苯中至少一种。
上述制备方法还包括如下提纯步骤：
在所述聚合反应完毕后，所得反应体系冷却后加入甲醇，室温下搅拌过滤，将所得沉淀用索氏提取器依次用甲醇、丙酮、正己烷抽提，抽提至无色后，除去小分子和催化剂，再用三氯甲烷抽提而得。
此外，上述所述的聚合反应的原料式1所示化合物也属于本发明的保护范围。
R的定义与前述式I中R的定义相同。
上述式I所示吡啶并三氮唑类发光聚合物作为半导体材料层在制备有机场效应晶体管中的应用也属于本发明的保护范围。
本发明还提供一种有机场效应晶体管，所述有机场效应晶体管的半导体材料层由式I所示吡啶并三氮唑类发光聚合物制成。
本发明具有如下优点：
1、原料为商业化产品，合成路线简单，产率高，还可以推广到各种直链或支链吡啶并三氮唑类发光聚合物的合成；
2、吡啶并三氮唑类发光聚合物的载流子迁移率及固态发光量子产率都很高，可用于制备有机场效应晶体管及发光晶体管；
3.以本发明吡啶并三氮唑类发光聚合物为半导体层制备的有机场效应晶体管有较高的空穴迁移率(最高为0.28cm2V-1s-1)和固态发光量子产率(最高为10％)，在有机场效应晶体管及发光晶体管中均具有良好的应用前景。
本发明合成了一种吡啶并三氮唑(简称PT)类新型受体及其发光聚合物，并研究了其发光特性及在OFETs中的应用。本发明的吡啶并三氮唑类聚合物进一步扩展了发光聚合物材料的种类，在有机光电子器件中具有良好的应用前景。
附图说明
图1为本发明制备I所示吡啶并三氮唑类聚合物结构式的路线图。(a)制备I-1所示聚合物PPT-TT-PT-2FBT的路线图；(b)制备I-2所示聚合物PPT-TT-PT-TT的路线图。
图2为本发明制备I所示吡啶并三氮唑类聚合物的紫外可见吸收光谱图。(a)I-1所示聚合物PPT-TT-PT-2FBT的紫外可见吸收光谱图；(b)I-2所示聚合物PPT-TT-PT-TT的紫外可见吸收光谱图。
图3为本发明制备I所示吡啶并三氮唑类聚合物的荧光发射光谱图。(a)I-1所示聚合物PPT-TT-PT-2FBT的荧光发射光谱图；(b)I-2所示聚合物PPT-TT-PT-TT的荧光发射光谱图。
图4为本发明制备I所示吡啶并三氮唑类聚合物的循环伏安曲线图。(a)I-1所示聚合物PPT-TT-PT-2FBT的循环伏安曲线图；(b)I-2所示聚合物PPT-TT-PT-TT的循环伏安曲线图。
图5为有机场效应晶体管的结构示意图。
图6为本发明制备I所示吡啶并三氮唑类聚合物为半导体层的聚合物场效应晶体管的输出特性曲线图和转移特性曲线图。(a)I-1所示聚合物PPT-TT-PT-2FBT为半导体层的聚合物场效应晶体管的输出特性曲线图(左图)和转移特性曲线图(右图)；(b)I-2所示聚合物PPT-TT-PT-TT为半导体层的聚合物场效应晶体管的输出特性曲线图(左图)和转移特性曲线图(右图)。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
本发明提供吡啶并三氮唑类发光聚合物的结构式如式I所示：
式I中，R为碳原子总数为1～60的直链或支链烷基，n为5～100之间的自然数；
Donor选自如下A类基团中的任意一种：
所述A类基团中，
表示取代的位置。
本发明还提供式1所示化合物：
式1中，R的定义同式I；具体可为5-癸基十五烷基。
上述式I所示吡啶并三氮唑类发光聚合物作为半导体材料层在制备有机场效应晶体管中的应用也属于本发明的保护范围。
以本发明的吡啶并三氮唑类发光聚合物为半导体层制备的有机场效应晶体管有较高的空穴迁移率(最高为0.28cm2V-1s-1)和固态发光量子产率(最高为10％)，在有机场效应晶体管及发光晶体管中均具有良好的应用前景。
实施例1、聚合物PPT-TT-PT-2FBT,R为5-癸基十五烷基(式I-1)
反应方程式如图1(a)所示。
(1)4,7-二溴-2H-[1,2,3]三唑并[4,5-c]吡啶
向100mL二口瓶中加入2,5-二溴-3,4-二氨基吡啶(4.00g，14.99mmol)，60mL醋酸，超声10min，然后一边搅拌，一边将溶于24mL蒸馏水的亚硝酸钠(1.55g，22.48mmol)滴入二口瓶中，30℃下反应24h。将产物用蒸馏水洗两遍，然后将产物过滤后转移至250mL圆底烧瓶中，加入约100mL乙醇并旋干(用乙醇带走水)，烘干得到白色固体4.05g。产率：97.12％。
结构表征数据如下：
质谱：ESI-MS:[M]-calcd for C5HBr2N4 -:276.85,found:276.90.
核磁氢谱和碳谱：1H NMR(400MHz,DMSO)δ8.49(m,1H).13C NMR(100MHz,DMSO)δ144.65,140.37,132.44,131.32,103.92.
(2)4,7-二溴-2-(5-癸基十五烷基)-2H-[1,2,3]三氮唑并[4,5-c]吡啶
向100mL二口瓶中加入4,7-二溴-2H-[1,2,3]三唑并[4,5-c]吡啶(2.00g,7.20mmol)，碳酸钾(1.99g，14.40mmol)，60mL N,N-二甲基甲酰胺溶液，通氩气保护。90℃下搅拌1h，逐滴加入5-癸基十五碘代烷(4.13g，8.64mmol)，90℃回流24h。用水和二氯甲烷萃取，无水硫酸钠干燥。将溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝3:1)，得到液体3.78g。产率：83.60％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+H]+calcd for C30H53Br2N4:629.26165,found:629.26092。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ8.34(s,1H),4.82(t,J＝9.2Hz,2H),2.15(m,J＝8.4Hz,2H),1.25–1.20(m,41H),0.87(t,J＝8.2Hz,6H).13C NMR(100MHz,CDCl3)δ146.44,143.36,141.70,132.71,108.09,58.04,37.19,33.52,32.93,31.91,30.47,30.09,29.68,29.64,26.34,26.63,23.61,22.67,14.09.
(3)2,5-双(7-溴-2-(5-癸基十五烷基)-2H-[1,2,3]三唑并[4,5-c]吡啶-4-基)噻吩并[3,2-b]噻吩
向100mL二口瓶中加入4,7-二溴-2-(5-癸基十五烷基)-2H-[1,2,3]三氮唑并[4,5-c]吡啶(1.5g,2.39mmol)，2,5-双(三甲基锡)噻吩并[3,2-b]噻吩(0.56g，1.20mmol)，催化剂二(三苯基膦)二氯化钯(0.043g，0.06mmol)和氯苯(60mL)，通氩气保护，然后将反应混合物加热到120℃反应24h。用加氟化钾的水溶液和二氯甲烷萃取，无水硫酸钠干燥。将溶液旋干后过柱(洗脱剂为石油醚：二氯甲烷＝1：1.5)，得到黄色固体1.20g。产率：81.04％。
结构表征数据如下：
质谱：HR-MALDI-TOF:[M+H]+calcd for C66H107Br2N8S2:1235.64064,found:1235.64012。
核磁氢谱和碳谱：1H NMR(400MHz,CDCl3)δ8.88(s,1H),8.54(s,1H),4.91(t,J＝8.8Hz,2H),2.22(m,J＝8.8Hz,2H),1.38–1.23(m,41H),0.87(t,J＝8.0Hz,6H).13C NMR(100MHz,CDCl3)δ147.07,145.40,144.97,143.37,143.20,138.31,123.85,105.74,57.73,37.28,33.58,33.03,31.92,30.59,30.11,29.70,29.64,29.35,26.68,23.72,22.67,14.09.
聚合物PPT-TT-PT-2FBT：
将式1所示2,5-双(7-溴-2-(5-癸基十五烷基)-2H-[1,2,3]三唑并[4,5-c]吡啶-4-基)噻吩并[3,2-b]噻吩(100.0mg,0.081mmol)、3,3’-二氟-5,5’-双(三甲基锡)-2,2’-联二噻吩(42.76mg,0.081mmol)、催化剂三(二亚苄基丙酮)二钯(2.25mg，0.0024mmol)、配体三(邻甲苯基)膦(5.84mg，0.019mmol)和氯苯(5mL)加入到反应瓶中，在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到125℃进行聚合反应48h。冷却后，加入100mL甲醇，室温下搅拌3h，过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷抽提得到最终产物99mg，产率95.85％。
结构表征数据如下：
分子量：GPC:Mn＝25.57kDa,PDI＝2.36，n＝20。
元素分析：Anal.calcd for C74H108F2N8S4:C 69.66,H 8.53,N 8.78,found:C69.04,H 8.45,N 8.41。
由上可知，该化合物结构正确，为式I-1所示化合物PPT-TT-PT-2FBT，结构式如下所示：
实施例2、聚合物PPT-TT-PT-TT，R为5-癸基十五烷基(式I-2)
其中R的定义与前述式1中R的定义相同。
反应方程式如图1(b)所示。
前三步同聚合物PPT-TT-PT-2FBT；
聚合物PPT-TT-PT-TT：
将式1所示2,5-双(7-溴-2-(5-癸基十五烷基)-2H-[1,2,3]三唑并[4,5-c]吡啶-4-基)噻吩并[3,2-b]噻吩(100.0mg,0.081mmol)、2,5-双(三甲基锡)噻吩并[3,2-b]噻吩(37.73mg,0.081mmol)、催化剂三(二亚苄基丙酮)二钯(2.25mg，0.0024mmol)、配体三(邻甲苯基)膦(5.84mg，0.019mmol)和氯苯(5mL)加入到反应瓶中，在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到125℃进行聚合反应48h。冷却后，加入100mL甲醇，室温下搅拌3h，过滤。得到的沉淀物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷抽提得到最终产物95mg，产率96.67％。
结构表征数据如下：
分子量：GPC:Mn＝19.91kDa,PDI＝2.35，n＝16。
元素分析：Anal.calcd for C72H108N8S4:C 71.24,H 8.97,N 9.23,found:C70.33,H 8.92,N 8.83。
由上可知，该化合物结构正确，为式I-2所示化合物PPT-TT-PT-TT，结构式如下所示：
实施例3、聚合物PPT-TT-PT-2FBT和PPT-TT-PT-TT的光学性能、电化学性能和场效应晶体管性能
(1)聚合物PPT-TT-PT-2FBT和PPT-TT-PT-TT的光学和电化学性能
图2为聚合物PPT-TT-PT-2FBT(图2(a))和PPT-TT-PT-TT(图2(b))在溶液和薄膜中的紫外可见吸收光谱图。
由图2可知，聚合物薄膜PPT-TT-PT-2FBT(图2(a))和PPT-TT-PT-TT(图2(b))的光学带隙分别为1.77eV和1.73eV(光学带隙根据公式Eg＝1240/λ计算，其中Eg为光学带隙，λ为紫外吸收曲线的边界值)。由图2可知，三个聚合物都具有比较强的分子内电荷转移峰，表明该聚合物分子间作用力较强。
图3为聚合物PPT-TT-PT-2FBT(图3(a))和PPT-TT-PT-TT(图3(b))的溶液(左边)和薄膜(右边)中的荧光发射光谱图。计算了材料的荧光量子产率(PLQY)，荧光量子产率的定义为荧光材料吸光后所发射的荧光光子数于所吸收的光子数的比值，该数值通常在0.01～1之间。
由图3可知，三个聚合物薄膜都具有比较宽的发射峰，说明聚合物在薄膜状态呈聚集态。经过计算可知PPT-TT-PT-2FBT的溶液态PLQY为19％，固态PLQY为10％；PPT-TT-PT-TT的溶液态PLQY为6％，固态为3％。
图4为聚合物PPT-TT-PT-2FBT(图4(a))和PPT-TT-PT-TT(图4(b))薄膜的循环伏安曲线。测定在CHI660c电化学工作站进行，用传统的三电极结构测试，铂为工作电极，铂丝为对电极，银/氯化银为参比电极，四丁基六氟磷酸铵作为支持电解质。测试在乙腈溶液中进行。循环伏安的条件为：扫描范围为-1.6～1.6伏特(vs.Ag/AgCl)，扫描速率为50毫伏每秒。两个聚合物都具有氧化峰和还原峰，可作为有机半导体材料。根据循环伏安曲线，聚合物PPT-TT-PT-2FBT和PPT-TT-PT-TT的HOMO能级分别为–5.40eV和–5.52eV，LUMO能级分别为–3.63eV和–3.79eV。
(2)聚合物PPT-TT-PT-2FBT和PPT-TT-PT-TT的场效应晶体管性能
图5为有机场效应晶体管的结构示意图，采用玻璃基底，在二次水、乙醇、丙酮中超声清洗于氮气吹干。以
的速度真空蒸镀5nm钛，30nm金作为源漏电极。实施例1、实施例2所得的聚合物为半导体层，将其浓度为10mg/ml的邻二氯苯溶液中通过偏心旋涂的方法在玻璃基底上形成有源层，厚度为25nm，并在150℃热台上退火10分钟。
随后在实施例1～实施例2所得的聚合物薄膜表面通过旋涂形成900纳米厚的聚甲基丙烯酸甲酯作为场效应管绝缘层，90℃除溶剂60分钟；在绝缘层上通过掩膜版热蒸镀110nm厚铝作为栅电极，完成场效应管制备。
在室温下用通过Keithley 4200SCS半导体测试仪测量了所制备的场效应器件的电学性能。决定OFET的性能的两个关键参数是：载流子的迁移率(μ)和器件的开关比(Ion/Ioff)。迁移率是指在单位电场作用下，载流子的平均漂移速度(单位是cm2 V-1s-1),它反映了在电场下空穴或电子在半导体中的迁移能力。开关比定义为：晶体管在“开”状态和“关”状态下的电流之比，它反映了器件开关性能的优劣。对于一个高性能的场效应晶体管，其迁移率和开关比应尽可能的高。
图6为聚合物PPT-TT-PT-2FBT(图6(a))和PPT-TT-PT-TT(图6(b))所制备的场效应晶体管的转移特性曲线(左边)和输出特性曲线(右边)。两个聚合物场效应晶体管显示出了明显的空穴传输特性，说明该类聚合物是一类P型材料。
载流子迁移率可由方程计算得出：
IDS＝(W/2L)Ciμ(VG–VT)2(饱和区)
其中，IDS为漏极电流，μ为载流子迁移率，VG为栅极电压，VT为阈值电压，W为沟道宽度，L为沟道长度，Ci为绝缘体电容。利用(IDS，sat)1/2对VG作图，并作线性回归，可由此回归线的斜率推算出载流子迁移率(μ)，由回归线与X轴的截点求得VT。
迁移率可以根据公式从转移曲线的斜率计算得出，上述各例中制备的聚合物场效应晶体管的器件性能如表1所示。三个聚合物的开关比可分别由图6(a)和图6(b)源漏电流的最大值与最小值之比得出。
实验结果表明该类聚合物是一类优异的新型高迁移率高发光材料。
表1聚合物场效应晶体管的器件性能
Claims (8)
1.式I所示聚合物：
式I中，R为碳原子总数为1～60的直链或支链烷基，n为5～100之间的自然数；
Donor选自如下A类基团中的任意一种：
所述A类基团中，
表示取代的位置。
2.根据权利要求1所述的式I所示聚合物，其特征在于：所述聚合物为PPT-TT-PT-2FBT或PPT-TT-PT-TT；
所述聚合物PPT-TT-PT-2FBT如式I-1所示，其中，n＝20：
其中R的定义与权利要求1中式I中R的定义相同；
所述聚合物PPT-TT-PT-TT如式I-2所示，其中，n＝16:
其中R的定义与权利要求1式I中R的定义相同。
3.式1所示化合物：
式1中，R的定义同权利要求1式I中R的定义。
4.制备式1所示化合物的方法，包括如下方法：
(1)在醋酸的水溶液中，式2所示2,5-二溴-3,4-二氨基吡啶与亚硝酸钠进行反应得到式3所示4,7-二溴-2H-[1,2,3]三氮唑并[4,5-c]吡啶；
(2)在碳酸钾存在的条件下，式3所示4,7-二溴-2H-[1,2,3]三氮唑并[4,5-c]吡啶与R-I所示碘代烷反应得到式4所示4,7-二溴-2-烷基-2H-[1,2,3]三氮唑并[4,5-c]吡啶；R-I中R的定义同式I；
式4中，R的定义同式I；
(3)在催化剂存在下，式4所示4,7-二溴-2-烷基-2H-[1,2,3]三氮唑并[4,5-c]吡啶与2,5-双(三甲基锡)噻吩并[3,2-b]噻吩发生偶联反应，得到式1所示化合物；
5.制备权利要求1或2所述的聚合物的方法，包括如下步骤：
在催化剂和配体存在的条件下，式1所示化合物与Me3Sn-Donor-SnMe3双甲基锡试剂经聚合反应，即得权利要求1或2所述的聚合物。
R的定义与权利要求1式I中R的定义相同。
6.根据权利要求5所述的方法，其特征在于：Me3Sn-Donor-SnMe3双甲基锡试剂选自如下化合物中的任意一种：
所述催化剂为四(三苯基膦)钯、二(三苯基膦)二氯化钯和三(二亚苄基丙酮)二钯中至少一种；
所述配体为三苯基膦、三(邻甲苯基)膦和三苯基砷中至少一种；
式1所示化合物与所述双甲基锡试剂的摩尔比为1：0.95～1.05；
式1所示化合物与所述催化剂的摩尔比为1：0.01～0.10；
式1所示化合物与所述配体的摩尔比为1：0.08～0.80；
所述聚合反应的温度为90～140℃，时间为2小时～80小时；
所述聚合反应在如下溶剂中进行：甲苯、氯苯和二甲苯中至少一种。
7.权利要求1或2所述的聚合物作为半导体材料层在制备有机场效应晶体管中的应用。
8.一种有机场效应晶体管，其半导体材料层由权利要求1或2所述的聚合物制成。
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