Effect of unwanted guest molecules on the stacking configuration of covalent organic frameworks: a periodic energy decomposition analysis

Wonanke, A.D.D. ORCID: 0000-0002-9066-2715 and Addicoat, M.A. ORCID: 0000-0002-5406-7927, 2022. Effect of unwanted guest molecules on the stacking configuration of covalent organic frameworks: a periodic energy decomposition analysis. Physical Chemistry Chemical Physics. ISSN 1463-9076

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Elucidating the precise stacking configuration of a covalent organic framework, COF, is critical to fully understand their various applications. Unfortunately, most COFs form powder crystals whose atomic characterisations are possible only through powder X-ray diffraction (PXRD) analysis. However, this analysis has to be coupled with computational simulations, wherein computed PXRD patterns for different stacking configurations are compared with experimental patterns to predict the precise stacking configuration. This task is often computationally challenging firstly because, computation of these systems mostly rely on the use of semi-empirical methods that need to be adequately parametrised for the system being studied and secondly because some of these compounds possess guest molecules, which are not often taken into account during computation. COF-1 is an extreme case in which the presence of the guest molecule plays a critical role in predicting the precise stacking configuration. Using this as a case study, we mapped out a full PES for the stacking configuration in the guest free and guest containing system using the GFN-xTB semi-empirical method followed by a periodic energy decomposition analysis using first-principles Density Functional Theory (DFT). Our results showed that the presence of the guest molecule leads to multiple low energy stacking configurations with significantly different lateral offsets. Also, the semi-empirical method does not precisely predict DFT low energy configurations, however, it accurately accounts for dispersion. Finally, our quantum-mechanical analysis demonstrates that electrostatic-dispersion model suggested Hunter and Sanders accurately describes the stacking in 2D COFs as opposed to the newly suggested Pauli-dispersion model.

Item Type: Journal article
Publication Title: Physical Chemistry Chemical Physics
Creators: Wonanke, A.D.D. and Addicoat, M.A.
Publisher: Royal Society of Chemistry (RSC)
Date: 13 June 2022
ISSN: 1463-9076
Rights: CC-BY. Open Access Article. Published on 13 June 2022. Downloaded on 6/16/2022 12:16:56 PM. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.View Article Online DOI: 10.1039/D2CP00017B.
Divisions: Schools > School of Science and Technology
Record created by: Linda Sullivan
Date Added: 21 Jun 2022 07:34
Last Modified: 21 Jun 2022 07:34
URI: https://irep.ntu.ac.uk/id/eprint/46471

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