Polychromatic femtosecond fluorescence studies of metal-polypyridine complexes in solution

► Femtosecond-resolved broadband fluorescence of Fe and Ru complexes in solution. ► Pump wavelength and solvent dependence of the fluorescence. ► Mirror-like image of t = 0 fluorescence with respect to the absorption. ► Fluorescence decays in ⩽30-45 fs due to intersystem crossing. ► Early intramolecular dynamics in ⩽10 fs.