Immobilisation interaction between photoactive Cu(I)-complexes and polymeric matrices studied computationally and experimentally

在可持续太阳能收集的框架内，我们使用了基于光活性的铜(I)4H-咪唑络合物的无贵金属体系，在牺牲供体的存在下，这些络合物可以被有效地光还原。然而，为了实现一个完全可持续的体系，即没有牺牲给体，我们研究了光活性的铜(I)4H-咪唑配合物在(功能)聚合物基质中的固定化，以期实现光氧化和光还原的耦合。本项目通过理论和实验相结合的方法，为理解阴离子铜(I)4H-咪唑配合物与阳离子聚合物基质之间的固定化相互作用迈出了第一步。分子动力学模拟被用来研究结合作用，并阐明聚合物基质对铜(I)配合物的电子性质的影响。这些研究得到了关于铜(I)4H-咪唑络合物与聚合物基质相互作用的光谱和电化学数据的补充。特别是，聚合物基质在光还原条件下的稳定性将被研究。只有理论和实验相结合，才能深入了解铜(I)络合物在聚合物基质中的主客体相互作用，从而有目的地发展铜(I)络合物和聚合物基质。

Within the frame of sustainable solar energy harvesting we use noble-metal free systems based on photoactive Cu(I) 4H-imidazolate complexes, which are efficiently photoreduced in the presence of a sacrificial donor. However, to achieve a fully sustainable system, i.e. without a sacrificial donor, we investigate the immobilisation of the photoactive Cu(I) 4H-imidazolate complexes in (functional) polymeric matrices for the prospective coupling of photooxidation and photoreduction. This project takes the first step towards an understanding of the immobilization interactions between anionic Cu(I) 4H-imidazolate complexes and cationic polymer matrices in a combined theoretical and experimental approach. Molecular dynamics simulations are used to study binding interactions and to elucidate the impact of the polymer matrix on the function-determining electronic properties of the Cu(I) complexes. These investigations are complemented by spectroscopically and electrochemically obtained data on the mutual interactions of the Cu(I) 4H-imidazolate complex and the polymer matrix. In particular, the stability of the polymer matrix under photoreductive conditions will be investigated. Only with the combination of theory and experiment an in-depth understanding of the host-guest interaction of Cu(I) complexes in polymeric matrices will be gained allowing for the purposeful development of both, the Cu(I) complex and the polymer matrix.