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Quantification of the Strength of π‐Noncovalent Interactions in Molecular Balances using Density Functional Methods

Nunar, Luka; Aliev, Abil E; (2022) Quantification of the Strength of π‐Noncovalent Interactions in Molecular Balances using Density Functional Methods. Chemistry–Methods 10.1002/cmtd.202200044. Green open access

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Abstract

Different molecular balances were designed previously to compare noncovalent interactions. However, some balances are difficult to synthesise and there is a need for developing a computational approach. In this work, we probe noncovalent interactions of π systems using DFT methods to assess their reliability in reproducing experimentally measured conformer populations. Based on our results, the PW6B95D3 functional performed best, followed by M11L and ωB97XD. Additionally, the simulation of the rotation of the hydroxyl group revealed stabilising OH⋯Alkyne and OH⋯Nitrile interactions that are difficult to identify experimentally. These methods were then applied to compare the strengths of sulfur⋯π interactions in molecules which have not been explored experimentally. Compared to the hydroxyl counterpart, the simulation of the thiol group rotation showed that the geometry of the conformer with the two sulfur lone pairs oriented towards the aromatic ring or the double bond is stabilised, suggesting that S(LP)⋯π interactions can be attractive in nature. The ability of sulfur to rearrange its electronic surrounding to form an attractive interaction with π systems, including those with either electron-donating or withdrawing groups, was also confirmed. Overall, the results show a promising future for both qualitative and quantitative assessments of the strengths of noncovalent interactions using selected DFT techniques.

Type: Article
Title: Quantification of the Strength of π‐Noncovalent Interactions in Molecular Balances using Density Functional Methods
Open access status: An open access version is available from UCL Discovery
DOI: 10.1002/cmtd.202200044
Language: English
Additional information: © 2022 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
Keywords: conformational analysis, density functional methods, noncovalent interactions, π-systems structure
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL
URI: https://discovery.ucl.ac.uk/id/eprint/10154279
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