Complexes of Rh(III), Ir(III), and Pt(IV) with Metallated 2-(n-Tolyl)pyridine, Ethylendiamine, Acetate, and Diethyldithiocarbamate Ligands

摘要

cis-CC Isomers of the [M(ptpy)2(L^L)](PF6)z complexes [M = Rh(III), Ir(III), Pt(IV); ptpy~- = deprotonated form of 2-(n-tolyl)pyridine, (L^L) = acetate, trifluoroacetate, or diethyldithiocarbamate anions, or ethylenediamine; z = 0, 1,2] were prepared and characterized by ~1H and ~(19)F NMR, IR, electronic absorption and emissions spectroscopy, and by voltammetry methods. The highest occupied and the lowest unoccupied molecular orbitals were assigned to d_π and π_(ptpy)* orbitals of the metal and the metallated ligand. Luminescence of the complexes in the visible spectral region was assigned to the spin-forbidden optical transition from the lowest energy state of the mixed nature (π_(ptpy)-π*_(ptpy/d_x-π_(ptpy)*).