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: Intramolecular Redox Isomerism of the Excited State Controlling the Photodelivery of NO.
Autor/es:
DE CANDIA ARIEL; MARCOLONGO JUAN; ETCHENIQUE ROBERTO; SLEP LEONARDO
Revista:
INORGANIC CHEMISTRY
Editorial:
AMER CHEMICAL SOC
Referencias:
Año: 2010 p. 6925 - 6925
ISSN:
0020-1669
Resumen:
 trans-[(NC)Ru(py)4( ¥ì-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 (¥ëmax = 518 nm; ¥åmax = 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 3 orders of magnitude smaller than that in the closely related cis-[RuL(NH3)4( ¥ì-pz)Ru(bpy)2(NO)]5©­ species (L = NH3 or pyridine, pz = pyrazine, bpy = 2,20-bipyridine; ¥õNO = 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©­ (¥õNO = (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.