Exploring Charge Redistribution at the Cu/Co6Se8 Interface

This study investigates the electronic interactions and charge redistribution at the dopant–support interface using a Cu/Co6Se8 cluster construct. Specifically, the redox cluster series [Cu3Co6Se8L6]n ([1-Cu3]n; n = 0, −1, −2, −3; L = Ph2PNTol–, Ph = phenyl, Tol = p-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-D3 symmetry. Paramagnetic 31P NMR spectroscopy and solution-phase magnetic measurements together with DFT calculations are employed to interrogate the electronic structure and spin-state changes across the [1-Cu3]3– to 1-Cu3 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.