Ballistic ΔS=2 Intersystem Crossing in a Cobalt Cubane Following Ligand-Field Excitation Probed by Extreme Ultraviolet Spectroscopy

Femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to probe the excited-state dynamics of the cobalt cubane [CoIII4O4](OAc)4(py)4 (OAc = acetate, py = pyridine), a model for water oxidation catalysts. After ligand-field excitation, intersystem crossing to a metal-centered quintet occurs in 38 fs. 30% of the hot quintet undergoes ballistic back-ISC directly to the singlet ground stat, with the remainder relaxing to a long-lived triplet.