INQUIMAE 12526
INSTITUTO DE QUIMICA, FISICA DE LOS MATERIALES, MEDIOAMBIENTE Y ENERGIA
Unidad Ejecutora - UE
artículos
Título:
Widely Differing Photochemical Behavior in Related Octahedral {Ru-NO}6 Compounds:
Autor/es:
DE CANDIA, A. G.; MARCOLONGO, J. P.; ETCHENIQUE, R.; SLEP, L. D.
Revista:
INORGANIC CHEMISTRY
Editorial:
AMER CHEMICAL SOC
Referencias:
Lugar: Wahington DC (USA); Año: 2010 vol. 49 p. 6925 - 6930
ISSN:
0020-1669
Resumen:
trans-[(NC)Ru(py)4(m-CN)Ru(py)4(NO)]3+ (py = pyridine) is a stable species in aqueous solution. It displays an intense absorption in the visible region of the spectrum (lmax = 518 nm; emax = 6100 M-1 cm-1), which turns this compound into a promising agent for the photodelivery of NO. The quantum yield for the photodelivery process resulting from irradiation with 455 nm visible light was found experimentally to be (0.06 ± 0.01) × 10-3 mol einstein−1, almost three orders of magnitude smaller than that in the closely related cis- [RuL(NH3)4(pz)Ru(bpy)2(NO)]5+ species (L = NH3 or pyridine, pz = pyrazine, bpy = 2,2-bipyridine fNO = 0.02-0.04 mol einstein-1 depending on L) and also much smaller than the one in the mononuclear compound trans-[ClRu(py)4(NO)]2+ (fNO = (1.63 ± 0.04) × 10-3 mol einstein−1). DFT computations provide an electronic structure picture of the photoactive excited states that helps to understand this apparently abnormal behavior.
