Direct Estimation of Aromatization Energy from 1H NMR and UV–Vis Absorption Data of Homodesmotic Molecules

Abstract

This study delves into the ring-opening reaction of two distinct diaryl-ring-pyran systems, referred to as drnp1 and drnp2, where the term ‘ring’ encompasses aromatic, nonaromatic, or antiaromatic motifs. These systems transform into the corresponding cis-ortho quinonoid systems, denoted as c-drnq1 and c-drnq2. Homodesmotic pairs (drnp1, drnp2) and (c-drnq1, c-drnq2) are categorized as (aromatic, nonaromatic), (aromatic, partially aromatic), (antiaromatic, nonaromatic), and (nonaromatic, nonaromatic), with their energy difference representing aromatization energy (Earoma). Using reliable density functional theory, Earoma is assessed for various aromatic and antiaromatic ring motifs, including borderline cases and nonaromatic structures. For example, benzene exhibits an Earoma of 23.4 kcal/mol, indicating 3.9 kcal/mol aromatic stabilization per CC bond, while cyclobutadiene shows −29.9 kcal/mol, indicating a 7.5 kcal/mol destabilization of the CC bond. This approach extends to evaluating global and local aromatic stabilization effects in polycyclic hydrocarbons, nonbenzenoid systems, and heterocyclic compounds. Additionally, variation in 1H NMR chemical shift (δavg) correlates with Earoma, suggesting that a −1.0 ppm shift corresponds to 24.2 kcal/mol aromatization energy. UV–vis absorption maxima difference (Δλavg) correlates linearly with Earoma, enabling direct assessment of aromatization energy from UV–vis spectra using suitable homodesmotic pairs. This comprehensive approach enhances our understanding of structural, energetic, and spectroscopic aspects of aromatic and antiaromatic systems.