Theoretical Studies on the Relationship between Aromaticity and Electron Transport Properties of Analogous [10]-Annulene Derivatives

Abstract

In the overall aromaticity of a molecular system, the magnitude of [Formula: see text]-aromaticity influences the degree of bond length averaging in the molecular geometry, while the magnitude of [Formula: see text]-aromaticity reflects the strength of [Formula: see text]-electron delocalization, subsequently affecting the electronic transport properties of the entire molecular system. Simultaneously, the aromaticity type of a molecular system is primarily determined by the symmetry of the innermost [Formula: see text] molecular orbitals. In this study, we conducted computational simulations of the aromaticity and electronic transport properties of compounds, including C8H8Cu2 with [Formula: see text]–[Formula: see text] delocalization effects and C12H8 with [Formula: see text]–[Formula: see text] delocalization effects, along with their Li derivatives. Based on calculated NICS values, ring current directions, molecular structural configurations and the symmetry of the innermost [Formula: see text] molecular orbitals, we clarified the aromaticity types of the molecular systems. Combined with the analysis of molecular electrical conductivity properties, we gained insights into the fundamental attributes of Li-bridge bonds in Li derivatives and the factors influencing electronic transport pathways. Consequently, we established a relationship between the aromaticity of molecular systems and their electronic transport properties. To a certain extent, a novel criterion for evaluating molecular aromaticity is proposed from the perspective of single-molecule electronics.