Spectroscopic and Electrochemical Investigation of Peripherally Diruthenated Complexes of octakis(benzylthio) and (methylthio)tetraazaporphyrinmagnesium(II)

Abstract

Four new trinuclear complexes were successfully synthesized through the dative binding of one unit of (bpy)2RuII and one unit of (phen)2RuII to the periphery of octakis(benzylthio)tetraazaporphyrinmagnesium(II) [Mg(OBTTAP)] and octakis(methylthio)tetraazaporphyrin- magnesium(II) ([Mg(OMTTAP)]). Spectroscopic techniques were used to perform an extensive characterization of the complexes, including an analysis of their fluorescence excitation/emission spectra and redox behaviours. Effective electronic interaction between the peripheral (bpy)2RuII/(phen)2RuII and [Mg(OBTTAP)] units is evidenced by the presence of these complexes. In cyclic voltammetry, the oxidation waves were slightly altered to a higher positive potential upon attaching a second Ru(II) unit in complexes 6, 7, 8 and 9.