Optoelectronic properties of diketopyrrolopyrrole homopolymers compared to donor-acceptor copolymers

Diketopyrrolopyrrole (DPP) is a component of a large number of materials used for optoelectronic applications. As it is exclusively used in combination with aromatic donors, the properties of its homopolymers are unknown. Because donor-acceptor character has been shown for other systems to reduce bandwidths, DPP homopolymers should have even larger conduction bands and better n-type conductivity than the thiophene-flanked systems, which have exceptional n-type conductivity and ambipolar character. Therefore, a theoretical study was carried out to elucidate the properties of the unknown DPP homopolymer. Calculations were done with density functional theory and with the complete active space self-consistent field method plus n-electron valence state perturbation theory for the dynamic correlation. Poly-DPP is predicted to have radical character and an extremely wide low-lying conduction band. If it were possible to produce this material, it should have unprecedented n-type conductivity and might be a synthetic metal. A comparison with various unknown donor-acceptor systems containing vinyl groups and thienyl rings with a higher concentration of DPP than the known copolymers reveals how donor-acceptor substitution reduces bandwidths and decreases electron affinities.