Complexes of Rh(III), Ir(III), and Pt(IV) with metallated 2-(n-tolyl)pyridine, ethylendiamine, acetate, and diethyldithiocarbamate ligands

Abstract

cis-C,C 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 19F NMR, IR, electronic absorption and emissions spectroscopy, and by voltammetry methods. The highest occupied and the lowest unoccupied molecular orbitals were assigned to dπ 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 (πptpy-π*ptpy/dx-π*ptpy).