Simulation of interlayer coupling for electroactive covalent organic framework design

Tanner M Leo; Megan Robbins; Alana Sullivan; Henry Thornes; Garrett Fitzsimmons; Alyssa Goodey; Tim Kowalczyk

doi:10.1063/5.0206246

Simulation of interlayer coupling for electroactive covalent organic framework design

J Chem Phys. 2024 May 14;160(18):184704. doi: 10.1063/5.0206246.

Authors

Tanner M Leo¹, Megan Robbins², Alana Sullivan¹, Henry Thornes², Garrett Fitzsimmons¹, Alyssa Goodey³, Tim Kowalczyk⁴

Affiliations

¹ Advanced Materials Science and Engineering Center, Western Washington University, Bellingham, Washington 98225, USA.
² Department of Chemistry and Advanced Materials Science and Engineering Center, Western Washington University, Bellingham, Washington 98225, USA.
³ Department of Chemistry and Institute for Energy Studies, Western Washington University, Bellingham, Washington 98225, USA.
⁴ Department of Chemistry, Advanced Materials Science and Engineering Center, and Institute for Energy Studies, Western Washington University, Bellingham, Washington 98225, USA.

PMID: 38721904
DOI: 10.1063/5.0206246

Abstract

Porous, stacked two-dimensional covalent organic frameworks (2D COFs) bearing semiconducting linkers can support directional charge transfer across adjacent layers of the COF. To better inform the current and possible future design rules for enhancing electron and hole transport in such materials, an understanding of how linker selection and functionalization affects interlayer electronic couplings is essential. We report electronic structure simulation and analysis of electronic couplings across adjacent linker units and to encapsulated species in functionalized electroactive 2D COFs. The detailed dependence of these electronic couplings on interlayer interactions is examined through scans along key interlayer degrees of freedom and through configurational sampling from equilibrium molecular dynamics on semiempirical potential energy surfaces. Beyond affirming the sensitivity of the electronic coupling to interlayer distance and orientation, these studies offer guidance toward linker functionalization strategies for enhancing charge carrier transport in electroactive 2D COFs.