Electrochemical and quantum chemical investigation of the CuI and CuII complexes with biquinolyl monomer and polymer ligands

Structural reorganization of polyamide (PA) and low-molecular-weight CuI and CuII complexes with biquinolyl (biQ) ligands during their mutual redox transformations in solution was studied using the electrochemical methods (cyclic voltammetry and preparative electrolysis) and quantum chemical DFT calculations. The influence of electronic factors and geometry distortions in the complexes on the ionization energy on going from CuI to CuII was evaluated in comparison. The catalytically active form of the [CuI(PA)L2]BF4 complex can be synthesized in situ from the stable tetrahedral complex [CuI(PA)2]BF4 by the series of successive redox transitions CuI → CuII → CuI accompanied by the loss of one biQ-containing macroligand.