Total non-lewis structures: An application to predict the stability and reactivity of linear and angular polyacenes

Abstract

In the present work, the total non-Lewis structure (TNLS) is introduced for describing the stability and reactivity of linear and angular polyacenes. TNLS of a molecule is derived from the natural bond orbital theory representing the antibonding orbitals and/or electron delocalization of π∗ orbitals. To verify this application, we obtained the TNLS values of thirteen linear and angular polyacenes and evaluated with other quantitative aromaticity probes based on reactivities, energetics, geometrics, and magnetic properties. Our results show that there is a remarkable second-order polynomial correlation between TNLS and seven popular global measures of aromaticity including hardness, resonance energy, aromatic stabilization energy, harmonic oscillator measure of aromaticity, magnetic susceptibility exaltation, global magnetic characteristics, and mean polarizability. By increasing the TNLS values of the systems the reactivity increases and stability decreases. It is worth mentioning that the angular polyacenes produce less TNLS values than the linear systems with the same number of benzene rings. Therefore, it can be stated that TNLS values confirmed with Clar’s rule which in general prove the angular polyacenes are more stable than linear ones.