Document Type

Article

Publication Date

2024

DOI

10.1039/D4CP03970J

Publication Title

Physical Chemistry Chemical Physics: PCCP

Volume

Article in Press

Pages

12 pp.

Abstract

Understanding the nature of π-stacking interactions is important to molecular recognition, self-assembly, and organic semiconductors. The stack bonding order (SBO) model of π-stacking has shown that the conformations of dimers occur when the combinations of monomer MOs are overall stack bonding in character. DFT calculations show that minima found on the potential energy surface for the π-stacked dimers of pentacene and perfluoropentacene occur when the dimer MOs are constructed from combinations of monomer MOs with an allowed SBO. An ex-amination of the MOs of π-stacked dimers extracted from X-ray structures of alkynyl derivatives like TIPS-pentacene pack at one or more of the minima expected to show similar MO patterns. The -stacking variability within these materials can be attributed to a balance between the minima allowed by SBO theory and steric effects within the lattice. The offset orientation of the pentacene cores observed in packing of these materials is attributed to the increased overlap of monomer lobes in the dimer and a reduction in two-orbital-four-electron repulsions. Charge mobility estimated from the frontier MOs of the dimer are related to the MO structure that favors PD conformations.

Rights

This article is licensed under a Creative Commons Attribution 3.0 Unported (CC BY 3.0) License.

Comments

This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.

Original Publication Citation

Bayse, C. A. (2024). Stack bonding in pentacene and its derivatives. Phys. Chem. Chem. Phys. Advance online publication. https://doi.org/10.1039/D4CP03970J

ORCID

0000-0002-3490-576X (Bayse)

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