Determinants of π-π Stacking Motifs in Polymers with Different Aromatic Side Groups

Liu S. Liu J. Wang Y. Zhong Y. Yong H. Huang Q.
10 March 2026 American Chemical Society

Macromolecules
2026 #59 Issue 5 2661 - 2668 pp.

In this study, all-atom molecular dynamics simulations, supported by Wide-Angle X-ray Scattering (WAXS) data, are used to investigate π-π stacking motifs in five polymers containing different aromatic side groups: polystyrene (PS), poly(2-vinylnaphthalene) (P2VN), poly(1-vinylnaphthalene) (P1VN), poly(4-vinylbiphenyl) (PVBP), and poly(acenaphthylene) (PACN). The probabilities of each π-π stacking motif (T-shaped, sandwich, and parallel displacement) formed between adjacent side groups are statistically evaluated for all polymers studied. The tendency to form stacking motifs of sandwich and parallel displacements shows a strong correlation with both higher torsional free energy barriers and greater spatial segregation of opposite electrostatic potentials in these polymers. Moreover, the results highlight the critical role of the overlap distance between aromatic side groups on adjacent chains in governing inter- or intra-chain π-π interactions.

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Polymer Research Institute, State Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu, 610065, China
School of Electrical Engineering and Electronic Information, Xihua University, Chengdu, 610039, China
Department of Chemical and Materials Engineering, School of Engineering and Digital Sciences, Nazarbayev University, 53 Kabanbay Batyr Avenue, Astana, 010000, Kazakhstan
Department of Molecules & Materials, MESA Institute, University of Twente, Enschede, 7500 AE, Netherlands
Institute Theory of Polymers, Leibniz-Institut für Polymerforschung Dresden e.V., Dresden, D-01069, Germany

Polymer Research Institute
School of Electrical Engineering and Electronic Information
Department of Chemical and Materials Engineering
Department of Molecules & Materials
Institute Theory of Polymers

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