Abstract
Phenalenyls (PLYs) are important synthons in many functional and electronic materials, which often display favorable molecule-to-molecule overlap for electron or hole transport. They also serve as a prototype for π-stacking pancake bonding based on two-electron multicenter bonding (2e/mc). Unexpected near-doubling of the binding energy is obtained for the positively charged PLY(2) (+) dimer with an effect similar to that seen for the positively charged olympicenyl (OPY) radical dimer. This charge effect is reversed for the perfluorinated (PF) dimers, and the negatively charged perfluorinated (PF) dimers PF-PLY(2) (-) and PF-OPY(2) (-) become strongly bound. Long-range interactions reflect these differences. Also surprising is that in this case the pancake bonding corresponds to single-electron (1e/mc) or a three-electron (3e/mc) multicenter bonding in contrast to the 2e/mc bonding that occurs for the neutral radical dimers. The strong preference for a large intermolecular overlap is maintained in these charged dimers. Importantly, the preference for π-bonding in the charged dimers compared to σ-bonding is strongly enhanced relative to the neutral PLY dimers.