Klingsiek Maximilian J, Vishnevskiy Yury V, Buth Julian, Lamm Jan-Hendrik, Neumann Beate, Stammler Hans-Georg, Mitzel Norbert W
Lehrstuhl für Anorganische Chemie und Strukturchemie (ACS), Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, D-33615, Bielefeld, Germany.
Angew Chem Int Ed Engl. 2025 Sep 15;64(38):e202509191. doi: 10.1002/anie.202509191. Epub 2025 Aug 12.
Presently, there is a notable interest in poly-Lewis acids (PLAs), their host-guest chemistry and their application in catalytic processes. The present study combines PLAs with redox-active dibenzo[a,e]cyclooctatetraene (dbCOT) units. dbCOT-based PLAs can be planarised by a two-electron reduction. The molecular structures of the reduced PLAs, studied by sc-XRD experiments and DFT calculations, show the formation of extended -systems. This -system extends to the Lewis acid functions and reduces their acidity. This allows a controlled release of complexed guest molecules. Oxidation regenerates the original Lewis acidity. Such reduction/oxidation cycles were also applied to an Al─P coordination polymer. sc-XRD shows the connectivity of the coordination polymer to remain unchanged, so that the polymer is stable in the neutral and reduced state. The possibility of switching such dbCOT-based PLAs and their adducts as well as the formed coordination polymers between two states with different structures and electronic compositions is of interest for the development of functional materials in the fields of electronics, optics and magnetism as well as for the development of switchable catalysts.
目前，人们对聚路易斯酸（PLAs）、它们的主客体化学及其在催化过程中的应用有着显著的兴趣。本研究将PLAs与具有氧化还原活性的二苯并[a,e]环辛四烯（dbCOT）单元相结合。基于dbCOT的PLAs可以通过双电子还原进行平面化。通过单晶X射线衍射（sc-XRD）实验和密度泛函理论（DFT）计算研究的还原态PLAs的分子结构表明形成了扩展的π-体系。这种π-体系延伸到路易斯酸官能团并降低了它们的酸度。这使得络合的客体分子能够被控制释放。氧化作用可使原始的路易斯酸度再生。这种还原/氧化循环也应用于一种铝-磷配位聚合物。sc-XRD表明配位聚合物的连接性保持不变，因此该聚合物在中性和还原态下是稳定的。对于电子、光学和磁学领域功能材料的开发以及可切换催化剂的开发而言，将这种基于dbCOT的PLAs及其加合物以及形成的配位聚合物在两种具有不同结构和电子组成的状态之间进行切换的可能性是令人感兴趣的。
