Magnetic anisotropies and relative aromaticities of pyrrole, pyrazole, imidazole and their N-methyl derivatives

Abstract

Experimental dipole moments, molar Kerr constants and molar Cotton-Mouton constants at 298 K and 633 nm are reported for pyrrole, pyrazole, imidazole and their N-methyl derivatives as solutes in dioxan. Analysis of the Kerr-effect data yields the effective polarizability anisotropies which are used to evaluate the molecular magnetic anisotropies from the Cotton-Mouton constants. The magnetic criterion of aromaticity is applied by estimating for each molecule the non-local contribution to the out-of-plane component of the magnetizability and the magnetic anisotropy. Electron delocalization in these molecules is significantly less than that exhibited by benzene: pyrrole and N-methylpyrrole, c. 70%; pyrazole and N-methylpyrazole, c. 65%; imidazole and N-methyl-imidazole, c. 60%. Approximately one-third of the observed magnetic anisotropy arises from localized contributions.