Light-induced spin crossover in Fe(II)-based complexes: The full photocycle unraveled by ultrafast optical and X-ray spectroscopies

The light-induced spin and structure changes upon excitation of the singlet metal-to-ligand charge transfer (1MLCT) state of Fe(II)-polypyridine complexes are investigated in detail in the case of aqueous iron(II)-tris-bipyridine ([FeII(bpy)3]2+) by a combination of ultrafast optical and X-ray spectroscopies. Polychromatic femtosecond fluorescence up-conversion, transient absorption studies in the 290-600nm region and femtosecond X-ray absorption spectroscopy allow us to retrieve the entire photocycle upon excitation of the 1MLCT state from the singlet low-spin ground state (1GS) as the following sequence: 1,3MLCT→5T→1GS, which does not involve intermediate singlet and triplet ligand-field states. The population time of the HS state is found to be ∼150fs, leaving it in a vibrationally hot state that relaxes in 2-3ps, before decaying to the ground state in 650ps. We also determine the structure of the high-spin quintet excited state by picosecond X-ray absorption spectroscopy at the K-edge of Fe. We argue that given the many common electronic (ordering of electronic states) and structural (Fe-N bond elongation in the high-spin state, Fe-N mode frequencies, etc.) similarities between all Fe(II)-polypyridine complexes, the results on the electronic relaxation processes reported in the case of [FeII(bpy)3]2+ are of general validity to the entire family of Fe(II)-polypyridine complexes. © 2009 Elsevier B.V.

Published in:
Coordination Chemistry Reviews, 254, 21-22, 2677-2686

 Record created 2010-10-04, last modified 2018-09-13

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