The IRCs for the rearrangement of (CH) 7 + , Naph and Phen plotted against C1–C4 internuclear distance, d , and H5–C5–C4–H4 dihedral angle, , show that the tropylium rings must become twisted to access the high-energy MT and DT isomers, which is facilitated by steric overcrowding. g , Plots of the energy of the twisted aromatic systems of fluoranthene, Naph and pentaphenyl-substituted Naph ( 2 ) relative to their planar geometries, E , obtained by performing a relaxed potential energy scan as the C4–C2–Cb–Cb' torsion angle is varied in 1 increments. See Fig. 2a for the structural formula of 2 . Two-dimensional plots of the data in f are shown in Supplementary Fig. 79 . All DFT calculations were performed at the B3LYP(GD3BJ)/6-31G(d)/CH 2 Cl 2 level of theory.
