X-ray absorption and emission spectroscopy of N2S2 Cu(<sc>ii</sc>)/(<sc>iii</sc>) complexes

This study investigates the influence of ligand charge on transition energies in a series of CuN2S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and K beta valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [Cu-II(HL1)] (HL1(2-) = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [Cu-II(HL2)] (HL2(2-) = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [Cu-III(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L2(3-) ligand stabilizes the Cu(III) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(III) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.