Substituent Effect on Triplet State Aromaticity of Benzene

Abstract

Density functional theory calculations have been performed to explore the substituent effect on benzene's structure and aromaticity upon excitation to the first triplet excited state (T1). Discussion is based on spin density analysis, HOMA (harmonic oscillator model of aromaticity), NICS (nucleus-independent chemical shift), ACID (anisotropy of the induced current density), and monohydrogenation free energies and shows that a large span of aromatic properties, from highly antiaromatic to strongly aromatic, could be achieved by varying the substituent. This opens up a possibility of controlling benzene's physicochemical behavior in its excited state, while molecular motion, predicted for several derivatives, could be of interest for the development of photomechanical materials.