Remarkable Electronic Effect on the meso-Tetra(thienyl)porphyrins

Complexes derived from meso-tetra(thienyl)porphyrins (TThP) and meso-tetra(pyridyl)porphyrin (TPyP) containing peripheral ruthenium complexes with general formulas {TPyP[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4, {TThP[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4, and {TThP-me-[RuCl(dppb)(5,5′-Mebipy)]4}(PF6)4 [5,5′-Mebipy = 5,5′-dimethyl-2,2′-bipyridine and dppb = 1,4-bis(diphenylphosphino)butane] were synthesized and characterized by spectroscopy techniques (1H- and 31P{1H}-NMR, IR, UV/vis, fluorescence, and electron paramagnetic resonance (EPR)), cyclic voltammetry, coulometry, molar conductivity, and elemental analysis. Voltammetry and UV/vis studies demonstrated differentiated electronic properties for ruthenium appended with TThP and TThP-me when compared to ruthenium appended with TPyP. The UV/vis analysis for the ruthenium complex derived from TThP and TThP-me, as well as the Soret and Q bands, characteristics of porphyrins, showed a band at 700 nm referring to the Ru → S electronic transition, and porphyrin TThP-me s...