Recebido em 28/01/2018; aceito em 17/04/2018; publicado na web em 22/05/2018 IMMOBILIZATION OF RUTHENIUM SCHIFF BASE COMPLEX IN THE METAL-ORGANIC FRAMEWORK UiO-67. Zirconium-based metal-organic framework, UiO-67, was synthesized and used as support for the immobilization of the [RuCl 2 (ENAPY)] (ENAPY = N,N'-bis(7-metyl-2-pyridylmethylene)-1,2-diiminoethane)). The immobilized system exhibited violetblue color. The {UiO-67/[RuCl 2 (ENAPY)]} was characterized by cyclic voltammetry, X-ray diffraction, UV-Vis, FTIR and X-ray photoelectron spectroscopy. The electrochemistry of the immobilized system is characterized by a reversible pair of waves at +0.40 V (vs NHE), ascribed to the Ru 3+/2+ redox process. The electronic spectrum of the immobilized system is characterized by bands at 520 and 380 nm ascribed to a ligand-to-metal charge-transfer transitions {Ru 2+

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The study of non-innocent redox behavior of ligands is important for the development of new catalysts and to comprehend the function of bioinorganic molecules in biochemical processes. In this work, we present a description of the non-innocent behavior of 1-(2′-pyridylazo)-2-naphtholate (pan) coordinated to ruthenium complexes. The synthesis and characterization of a series of [Ru(pan) (PPh 3 )(L)]PF 6 complexes [where L = 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (dmbpy), and 1,10-phenanthroline (phen)] are presented. UV-vis analyses of the studied ruthenium complexes show intense absorptions from intraligand π-π* and metal-to-ligand charge-transfer transitions bands in the visible region. This observation shows a significant contribution of the pan ligand in all electronic transitions and is the indicative of non-innocent behavior. Theoretical calculations were carried out to support the UV-vis spectral assignments. Non-innocent behavior of pan was observed and confirmed using the electrochemical parameter E L (L) and by electrochemical studies. The pan ligand is non-innocent and can be modulated by donor and acceptor character of the other ligands present in the coordination sphere of the complex.