Effect of BN substitution on structure, reactivity and spectroscopic properties of polyarylenevinylene systems: A computational insight

Abstract

Linearly conjugated systems in organic chemistry reveal the intriguing relationship between structure and electronic properties. Such systems, characterized by alternating single and multiple bonds, possess unique electronic traits with practical applications in organic electronics. Carbon‐bridged oligophenylenevinyles (COPVs) are promising candidates for enhanced charge transport. However, their synthesis efficiency poses challenges. Heteroatom substitution, particularly BN dative bonding, enhances stability without compromising electronic properties. DFT calculations performed on Carbon‐bridged naphthylmethyl vinylenes (CNMVs) and Boron and carbon bridged quinolylmethyl vinylenes (BQMVs) reveal altered absorption and vibrational behaviors due to BN substitution. Hirshfeld charge analysis and dual descriptor assessment highlight modified electrophilic and nucleophilic regions, showcasing adaptability in functional groups. BN substitution also resulted in a notable decrease in the HOMO–LUMO gap of both CNMV1 and CNMV2. In CNMV1, the HOMO–LUMO gap dropped from 3.75 to 3.37 eV, and in CNMV2, the HOMO–LUMO gap narrowed from 3.16 to 2.80 eV. This research explores the structural and electronic aspects of conjugated molecules, emphasizing the potential of heteroatom substitution for tailored applications in organic electronics.