Theoretical study on the poly(m-phenylene) derivatives with lower HOMO–LUMO gaps

Abstract Poly(m-phenylene) (PMP) has received great attention for its rigid-rod backbone structure, high thermal stability, and promising electronic properties due to its broken conjugation. In this paper we report a theoretical study based on density functional theory calculations on the synthesis of PMP derivatives with lower HOMO–LUMO gaps (HLGs). Our calculations reveal an effective approach to obtain PMP derivatives with lower HLGs arising from decreased LUMO levels significantly via bridging the phenyl rings by C = X fragments (X = S, Se).