Vibrational Coherence Spectroscopy Identifies Ultrafast Branching in an Iron(II) Sensitizer

The introduction of N-heterocyclic carbene ligands has greatly increased the lifetimes of metal-to-ligand charge transfer states (MLCT) in iron­(II) complexes, making them promising candidates for photocatalytic applications. However, the spectrally elusive triplet metal-centered state (³MC) has been suggested to play a decisive role in the relaxation of the MLCT manifold to the ground state, shortening their lifetimes and consequently limiting the application potential. In this work, time-resolved vibrational spectroscopy and quantum chemical calculations are applied to shed light on the ³MCs’ involvement in the deactivation of the MLCT manifold of an iron­(II) sensitizer. Two distinct symmetric Fe–L breathing vibrations at frequencies below 150 cm^–1 are assigned to the ³MC and ³MLCT states by quantum chemical calculations. On the basis of this assignment, an ultrafast branching directly after excitation forms not only the long-lived ³MLCT but also the ³MC as an additional loss channel.