INVESTIGADORES
FAGALDE Florencia
artículos
Título:
Spectroscopic, electrochemical and computational studies of rhenium(I) and ruthenium(II) complexes incorporating the novel tetradentate ligand 1,4-bis(4-(4??-methyl)-2,2??-bipyridyl)-2,3-diaza-1,3-butadiene (BBDB) and its derivatives
Autor/es:
CATTANEO, MAURICIO; VERGARA MÓNICA M.; GARCÍA POSSE MÓNICA E.; FAGALDE, FLORENCIA; PARELLA, TEODOR; KATZ, NÉSTOR E
Revista:
POLYHEDRON
Editorial:
PERGAMON-ELSEVIER SCIENCE LTD
Referencias:
Lugar: Amsterdam; Año: 2014 vol. 70 p. 20 - 28
ISSN:
0277-5387
Resumen:
The novel tetradentate ligand 1,4-bis(4-(4?-methyl)-2,2?-bipyridyl)-2,3-diaza-1,3-butadiene (BBDB) was synthesized and characterized by spectroscopic techniques. New complexes of Re and Ru of formulae: [Re(BBDB)(CO)3(Cl)], [(CH3CN)(CO)3Re(l-BBDB)Re?(CO)3(CH3CN)]2+, [(bpy)2Ru-(l-BBDB)Ru(bpy)2]4+, [(NH3)4Ru(l-BBDB)?Ru(NH3)4]4+ (bpy = 2,2?-bipyridine) and complexes of Ru with 4-Me-4?-CO2H-bpy (=4-methyl-4?-carboxylic acid-2,2?-bipyridine) ? the hydrolyzed derivative of BBDB ? of formulae: [(Ru(4-Me-4?-CO2H-bpy)(bpy)2]2+ and [Ru(4-Me-4?--CO2H-bpy)(CN)4]2 were prepared and characterized by spectroscopic, electrochemical and computational techniques. The disclosed enhanced electronic coupling in the mixed-valent complex with ruthenium ammines can be explained by the electronic delocalization imposed by the AC@NAN@CA backbone. DFT and TD-DFT calculations can predict the optical properties and electronic structures of the reported complexes and comparisons with calculations performed on previously reported complexes with 4-pyridinaldazine can account for their photophysical behaviour.