Computational investigation of intramolecular reorganization energy in diketopyrrolopyrrole (DPP) derivatives

Abstract

Intramolecular reorganization energy (RE) of molecules derived from the diketopyrrolopyrrole (DPP) unit has been studied using B3LYP/6-31G(d,p) theory. It was found that the replacement of the oxygen atoms with sulfur in the DPP unit led to a smaller RE for both the hole and electron transfer processes. One disadvantage of the sulfur replacement is the twist of the conjugated backbone, which might impair the π − π interactions in the solid state. The RE calculated from the adiabatic potential energy surfaces and that derived from the normal mode analysis agreed well for both systems. Electronic structure data showed that the replacement of oxygen atoms with sulfur in the DPP unit might lead to the development of ambipolar compounds with low RE.