Synthesis and Structure‐Property Relationships in Regioisomeric Alternating Borane‐Terthiophene Polymers
Synthesis and Structure‐Property Relationships in Regioisomeric Alternating Borane‐Terthiophene Polymers
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区域异构交替硼烷—三联噻吩聚合物的合成及结构—性能关系
DOI：
10.1002/chem.202203619
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Jäkle, Frieder
中科院分区：
文献类型：
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作者：
Alahmadi, Abdullah F.;Yin, Xiaodong;Lalancette, Roger A.;Jäkle, Frieder
主链含硼π共轭聚合物在有机电子、传感和成像应用中具有吸引力。制备交替的三噻吩-硼烷聚合物，并检查共辄连接体的区域异构连接的影响和侧芳基（2，4，6_三叔丁基苯基，Mes*; 2，4，6_三（三氟甲基）苯基，FMes）的电子效应的变化。Pd 2dba 3/P（t-Bu）3催化的芳基双（2-噻吩基）硼烷和芳基双（3-噻吩基硼烷）与2，5-双（三甲基甲锡烷基）噻吩在120 °C下的Stille聚合得到具有可观分子量的聚合物，但MALDI-TOF MS分析显示出异常突出的均偶联的证据。这些缺陷可以通过在100 °C下使用溴化而不是碘化单体、更受阻的2，5-双（三正丁基甲锡烷基）噻吩作为共聚单体和Pd 2dba 3/P（o-tol）3作为催化剂来抑制。在这些条件下，根据MALDI-TOF MS分析，优先形成具有n =3-10个重复单元的大环物质。光物理研究揭示了区域化学和侧芳基的性质对吸收和发射的显著影响，分别产生橙子、黄色绿色、蓝色绿色和蓝色发射材料。通过对双（三噻吩）模型体系的DFT计算，合理化的电子效应。
Main‐chain boron‐containing π‐conjugated polymers are attractive for organic electronic, sensing, and imaging applications. Alternating terthiophene‐borane polymers were prepared and the effects of regioisomeric attachment of the conjugated linker and variations in the electronic effect of the pendent aryl groups (2,4,6‐tri‐tert‐butylphenyl, Mes*; 2,4,6‐tris(trifluoromethyl)phenyl, FMes) examined. Pd2dba3/P(t‐Bu)3‐catalyzed Stille polymerization of arylbis(2‐thienyl)borane and arylbis(3‐thienylborane) with 2,5‐bis(trimethylstannyl)thiophene at 120 °C gave polymers with appreciable molecular weight but MALDI‐TOF MS analyses showed evidence of unusually prominent homocoupling. These defects could be suppressed by using brominated rather than iodinated monomers, more hindered 2,5‐bis(tri‐n‐butylstannyl)thiophene as comonomer, and Pd2dba3/P(o‐tol)3as the catalyst at 100 °C. Under these conditions, macrocyclic species withn=3–10 repeating units formed preferentially according to MALDI‐TOF MS analyses. Photophysical studies revealed a prominent effect of the regiochemistry and the nature of the pendent aryl groups on the absorption and emission, giving rise to orange, yellow‐green, blue‐green, and blue emissive materials respectively. The electronic effects were rationalized through DFT calculations on bis(terthiophene) model systems.