Abstract A new series of conjugated thiophene-based poly(azomethine)s (PAZThAs) containing tetraphenylsilane (TPS) cores and thiophene or bithiophene moieties along the backbone were obtained from silicon-containing diamines and commercial 2,5-thiophenedicarboxaldehyde and 2,2′-bithiophene-5,5′-dicarboxaldehyde through high-temperature polycondensation reactions. Solution-processable polymers were obtained in high yields (74–96%), high average molecular weight (Mw: 2,900–22,200 g/mol), with adequate polydispersity (closed to 2), and high thermal stability (T10%: 326–488 °C). The thiophene-based PAZ showed suitable absorptions and emissions in the UV–vis range with moderate Stokes shifts (46 to 65 nm). The lower band gap value was observed for PAZ2ThA2 (1.98 eV) that is closely similar to polythiophene derivates studied in polymer solar cells (PSCs). The calculated HOMO energies values are in the range of −5.82 eV to −5.42 eV, while the LUMO energies ranging from −3.56 to −3.39 eV. Compared to fully π-conjugated PThs, the PAZThAs tend to possess higher LUMO energies and similar HOMO energies, which is attributable to the electronic influence of the TPS-cores. This study motivates future researches on TPS building-blocks based PAZs.

中文翻译：

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新的基于噻吩的聚（偶氮甲碱）在其骨架上带有四苯基硅烷部分。光学、电子、热学特性和理论计算

摘要 从含硅二胺和商业 2,5-噻吩二甲醛和 2,2' 中获得了一系列新的共轭噻吩基聚（偶氮甲碱）（PAZThAs），其中含有四苯基硅烷（TPS）核和沿骨架的噻吩或联噻吩部分。 -bithiophene-5,5'-二甲醛通过高温缩聚反应。以高产率 (74–96%)、高平均分子量 (Mw: 2,900–22,200 g/mol)、足够的多分散性 (接近 2) 和高热稳定性 (T10%: 326– 488°C）。基于噻吩的 PAZ 在 UV-vis 范围内显示出合适的吸收和发射，具有中等斯托克斯位移（46 至 65 nm）。观察到 PAZ2ThA2 的带隙值较低 (1. 98 eV)，这与在聚合物太阳能电池 (PSC) 中研究的聚噻吩衍生物非常相似。计算出的 HOMO 能量值在 -5.82 eV 到 -5.42 eV 的范围内，而 LUMO 能量值在 -3.56 到 -3.39 eV 的范围内。与完全 π 共轭 PTh 相比，PAZThAs 往往具有更高的 LUMO 能量和类似的 HOMO 能量，这归因于 TPS 核的电子影响。这项研究激发了未来对基于 TPS 构建块的 PAZ 的研究。