Kinetics of formation of charge transfer complexes of poly(vinyl pyridines) with iodine, 7,7′8,8′‐tetracyanoquinodimethane and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone by electronic spectroscopic studies

Abstract

The kinetics of formation of charge transfer complexes of poly(4‐vinyl pyridine), poly(2‐vinyl pyridine), and poly(2‐vinyl pyridine‐co‐styrene) with iodine, 7,7′,8,8′‐tetracyanoquinodimethane and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone has been studied using electronic absorption spectroscopy. The charge transfer complexes of analogous low molecular weight donors, namely 2‐ and 4‐picolines with the same set of acceptors have also been investigated for comparison. The composition and the equilibrium constants of the charge transfer complexes have been obtained. The equilibrium constant of the polymeric complexes is found to be higher than that of analogous complexes of the low molecular weight donors. A new method for determining the rate constants of the association and dissociation of the equilibrium involving the charge transfer complex formation has been proposed. The rate constants vary with the concentration of the acceptor. It indicates that the charge transfer complexes undergo a further reaction and hence the observed rate constants are not true but apparent rate constants. The charge transfer complexes have also been investigated by electron paramagnetic resonance spectroscopy.