Visualizing electron delocalization in contorted polycyclic aromatic hydrocarbons

Abstract

Electron delocalization in contorted polycyclic aromatic hydrocarbon (PAH) molecules was examined through 3D isotropic magnetic shielding (IMS) contour maps built around the molecules using pseudo-van der Waals surfaces. The resulting maps of electron delocalization provided an intuitive, yet detailed and quantitative evaluation of the aromatic, non aromatic, and antiaromatic character of the local and global conjugated cyclic circuits distributed over the molecules. An attractive pictural feature of the 3D IMS contour maps is that they are reminiscent of the Clar π-sextet model of aromaticity. The difference in delocalization patterns between the two faces of the electron circuits in contorted PAHs was clearly visualized. For π-extended contorted PAHs, some splits of the π system resulted in recognizable patterns typical of smaller PAHs. The differences between the delocalization patterns of diastereomeric chiral PAHs could also be visualized. Mapping IMS on pseudo-van der Waals surfaces around contorted PAHs allowed visualization of their superimposed preferred circuits for electron delocalization and hence their local and global aromaticity patterns.