Metallica: A large contraction of the PtPt bond in the triplet excited state of the photoreactive [Pt2(P2O5H2)4]4- ion is determined by time-resolved X-ray absorption spectroscopy (see picture). The strengthening of the PtPt interaction is accompanied by a weakening of the ligand coordination bonds, resulting in an elongation of the platinum-ligand bond that is determined for the first time.