Understanding the correlation between electronic coupling and energetic stability of molecular crystal polymorphs: The instructive case of quinacridone

TL;DR

This study investigates how electronic coupling relates to the energetic stability of different quinacridone crystal forms, revealing that orbital interactions and repulsion influence the preferred molecular arrangements for optimal charge transport.

Contribution

The paper provides a detailed analysis of the correlation between electronic coupling and energetic stability in quinacridone polymorphs, introducing a model to compare displacement effects systematically.

Findings

Electronic coupling is minimized by specific molecular displacements.

Pauli repulsion and orbital rehybridization drive structural preferences.

Design strategies should include functional groups to control crystal packing.

Abstract

A crucial factor determining charge transport in organic semiconductors is the electronic coupling between the molecular constituents, which is heavily influenced by the relative arrangement of the molecules. This renders quinacridone, with its multiple, structurally fundamentally different polymorphs and their diverse intermolecular interactions an ideal test case for analyzing the correlation between the electronic coupling in a specific configuration and the configuration's energetic stability. To provide an in-depth analysis of this correlation, starting from the $\alpha$-polymorph of quinacridone, we also construct a coplanar model crystal. This allows us to systematically compare the displacement-dependence of the electronic coupling with that of the total energy. In this way, we identify the combination of Pauli repulsion and orbital rehybridization as the driving force steering the system towards a structure in which the electronic coupling is minimal (especially for the valence band and at small displacements). The general nature of these observations is supported by equivalent trends for an analogous pentacene model system. This underlines that the design of high-performance materials cannot rely on the "natural" assembly of the $\pi$-conjugated backbones of organic semiconductors into their most stable configurations. Rather, it must include the incorporation of functional groups that steer crystal packing towards more favorable structures, where aiming for short-axis displacements or realizing comparably large long-axis displacements appear as strategies worthwhile exploring.