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Updated: Jun 29, 2025

Anionic Polymerization of an Amphiphilic Copolymer for Preparation of Block Copolymer Micelles Stabilized by π-π Stacking Interactions
Published on: October 10, 2016
Structure and Bonding in π-Stacked Perylenes: The Impact of Charge on Pancake Bonding
Rameswar Bhattacharjee1, Henry Jervis1, Megan E McCormack2
1Department of Chemistry and Institute of Soft Matter, Georgetown University, 37th and O Streets, NW, Washington, D.C. 20057-1227, United States.
Abstract:
Perylene (PER) is a prototype of polycyclic aromatic hydrocarbons (PAHs), which play a pivotal role in various functional and electronic materials due to favorable molecule-to-molecule overlaps, which enhance electronic transport. This study provides guidelines regarding the impact of molecular charge on pancake bonding, a form of strong π-stacking interaction. Pancake bonding significantly boosts interaction energies within the monopositive dimer ([(C20H12)2]•+ or PER2+), crucial for stabilizing aggregation and crystal formation. We discovered energetically feasible sliding and rotation pathways within the [(C20H12)2]•+ dimer, connecting different configurations found in the Cambridge Structural Database (CSD). The dimer's charge profoundly influences the pancake bond order (PBO) and the strength and structural preferences of pancake bonding. The most stable configuration is found in the monocationic state (PER2+), featuring a pancake bond order of 1/2 with one-electron multicenter bonding (1e/mc) with similar characteristics for charge -1. Increasing the total charge of the dimer to +2 or -2 leads to an unstable local minimum. Diverse distribution of pancake bonding types present in crystal structures is interpreted with modeling based on dimer computations with varying charges.
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