title: Photo-induced spin-state conversion in solvated transition metal complexes probed via time-resolved soft X-ray spectroscopy.
abstract: Solution-phase photoinduced low-spin to high-spin conversion in the Fe(II) polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)(3) is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) --> (1)MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L(2)- and L(3)-edges were observed concomitant with formation of the transient high-spin (5)T(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of approximately 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 A increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.
authors.affiliation: Ultrafast X-ray Science Lab, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. nhuse@lbl.gov
authors.forename: Nils
authors.initials: N
authors.lastname: Huse
authors.forename: Tae Kyu
authors.initials: TK
authors.lastname: Kim
authors.forename: Lindsey
authors.initials: L
authors.lastname: Jamula
authors.forename: James K
authors.initials: JK
authors.lastname: McCusker
authors.forename: Frank M F
authors.initials: FM
authors.lastname: de Groot
authors.forename: Robert W
authors.initials: RW
authors.lastname: Schoenlein