Dizzy cooling: Femtosecond excitation of the singlet states of aqueous [FeII(bpy)3]2+ (bpy=2,2-bipyridine) leads to the formation of a vibrationally hot quintet state that exhibits wave-packet dynamics arising from a chelate-ring and bending mode. The vibrational relaxation involves at least two modes: the FeN stretching mode (see picture) and the coherently excited chelate-ring and bending mode, which relax on different time scales.