Exploring Charge Redistribution at the Cu/CoSe Interface.

This study investigates the electronic interactions and charge redistribution at the dopant-support interface using a Cu/CoSe cluster construct. Specifically, the redox cluster series [CuCoSeL] ([-Cu]; = 0, -1, -2, -3; L = PhPNTol, Ph = phenyl, Tol = -tolyl) spanning four distinct oxidation states is synthesized and characterized using a multitude of techniques, including multinuclear NMR, UV-vis, XANES, and X-ray crystallography. Structural investigations indicate that the clusters are isostructural and chiral, adopting a pseudo- symmetry. Paramagnetic P NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [-Cu] to -Cu redox series, revealing that the copper edge sites retain a +1 oxidation state while the Co/Se core becomes increasingly oxidized, yielding a highly zwitterionic cluster.