Novozhilova Maria, Polozhentseva Julia, Karushev Mikhail
Ioffe Physical-Technical Institute of the Russian Academy of Sciences (Ioffe Institute), 26 Polytekhnicheskaya Str., 194021 St. Petersburg, Russia.
Independent Researcher, Astana 020000, Kazakhstan.
Polymers (Basel). 2023 Feb 23;15(5):1127. doi: 10.3390/polym15051127.
Conductive and electrochemically active polymers consisting of Salen-type metal complexes as building blocks are of interest for energy storage and conversion applications. Asymmetric monomer design is a powerful tool for fine-tuning the practical properties of conductive electrochemically active polymers but has never been employed for polymers of M(Salen)]. In this work, we synthesize a series of novel conducting polymers composed of a nonsymmetrical electropolymerizable copper Salen-type complex (Cu(3-MeOSal-Sal)en). We show that asymmetrical monomer design provides easy control of the coupling site via polymerization potential control. With in-situ electrochemical methods such as UV-vis-NIR (ultraviolet-visible-near infrared) spectroscopy, EQCM (electrochemical quartz crystal microbalance), and electrochemical conductivity measurements, we elucidate how the properties of these polymers are defined by chain length, order, and cross-linking. We found that the highest conductivity in the series has a polymer with the shortest chain length, which emphasizes the importance of intermolecular iterations in polymers of [M(Salen)].
由Salen型金属配合物作为结构单元组成的导电和电化学活性聚合物在能量存储和转换应用中具有重要意义。不对称单体设计是微调导电电化学活性聚合物实际性能的有力工具，但从未应用于[M(Salen)]聚合物。在这项工作中，我们合成了一系列由非对称可电聚合的铜Salen型配合物（Cu(3-MeOSal-Sal)en）组成的新型导电聚合物。我们表明，不对称单体设计通过控制聚合电位可轻松控制偶联位点。通过原位电化学方法，如紫外-可见-近红外（UV-vis-NIR）光谱、电化学石英晶体微天平（EQCM）和电化学电导率测量，我们阐明了这些聚合物的性能是如何由链长、有序度和交联来定义的。我们发现该系列中电导率最高的聚合物具有最短的链长，这强调了[M(Salen)]聚合物中分子间迭代的重要性。
