Pancake Bonding: An Unusual Pi-Stacking Interaction

A category of parallel pi-stacking interaction, termed pancake bonding, is surveyed. The main characteristics are: the interaction occurs among radicals with highly delocalized pi-electrons in their singly occupied molecular orbitals (SOMOs), the contact distances in the pi-stacking direction are shorter than the typical van der Waals distances, and the stabilization obtained by the bonding combination of the SOMO orbitals leads to direct atom-to-atom overlap with strong orientational preferences. These atypical intermolecular interactions contain a component of electron sharing between the radicals that can be viewed as covalent-like. Pancake bonded dimers characteristically have low-lying singlet and triplet states and show characteristic interlayer vibrational modes. Pancake bonded aggregates serve as molecular components in many conducting and other functional organic materials. The role of van der Waals (vdW) interactions in pancake bonded dimers, chains, and other aggregates is different from closed shell vdW aggregates: here the Pauli repulsions reduce the attractive dispersion interaction significantly. Fluxionality between pi- and sigma-bonded aggregates often occur in the context of pancake bonding. Both experimental and computational aspects are reviewed.