title: Spectroscopic signatures of ligand field states in {Ru(II)(imine)} complexes.
abstract: Ligand field (LF) states have been present in discussions on the photophysics and photochemistry of ruthenium-iminic chromophores for decades, although there is very little documented direct evidence of them. We studied the picosecond transient absorption (TA) spectroscopy of four {Ru(II)(imine)} complexes that respond to the formula trans-[Ru(L)4(X)2], where L is either pyridine (py) or 4-methoxypyridine (MeOpy) and X is either cyanide or thiocyanate. Dicyano compounds behave as most ruthenium polypyridines and their LF states remain silent. In contrast, in the dithiocyanate complexes we found clear spectroscopic evidence of the participation of LF states in the MLCT decay pathway. These states are of donor and acceptor character simultaneously and this is manifested in the presence of MLCT and LMCT transient absorption bands of similar energy. Spectroelectrochemical techniques supported the interpretation of the absorption features of MLCT states, and DFT methods helped to assign their spectroscopic signatures and provided strong evidence on the nature of LF states.
authors: Departamento de Química Analítica, Inorgánica y Química Física, INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina. jhodak@qi.fcen.uba.ar.
authors: Alejandro
authors: A
authors: Cadranel
authors: German E
authors: GE
authors: Pieslinger
authors: Pornthip
authors: P
authors: Tongying
authors: Masaru K
authors: MK
authors: Kuno
authors: Luis M
authors: LM
authors: Baraldo
authors: José H
authors: JH
authors: Hodak