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In Cu(I)2(HCO2)3-, the system relaxes to a local minimum on an excited state potential energy surface and might undergo fluorescence or reach a conical intersection to the ground state, in both cases providing substantial energy for statistical decomposition. Alternatively, a Cu(II)(HCO2)3Cu(- biradical structure is formed in the excited state, which gives rise to the photochemical loss of a neutral copper atom. © 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.Photochemistry has emerged in the last few years as a powerful tool for