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Lookup NU author(s): Surabhi Gupta, Charlotte Cummings, Dr Nick WalkerORCiD, Professor Elangannan Arunan
This is the authors' accepted manuscript of an article that has been published in its final definitive form by Royal Society of Chemistry, 2024.
For re-use rights please refer to the publisher's terms and conditions.
The microwave spectra of five isotopologues of phenylacetylene⋯methanol complex, C6H5CCH⋯CH3OH, C6H5CCH⋯CH3OD, C6H5CCH⋯CD3OD, C6H5CCD⋯CH3OH and C6H5CCH⋯13CH3OH, have been observed through Fourier transform microwave spectroscopy. Rotational spectra unambiguously unveil a specific structural arrangement characterised by dual interactions between the phenylacetylene and methanol. CH3OH serves as a hydrogen bond donor to the acetylenic π-cloud while concurrently accepting a hydrogen bond from the ortho C–H group of the PhAc moiety. The fitted rotational constants align closely with the structural configuration computed at the B3LYP-D3/aug-cc-pVDZ level of theory. The transitions of all isotopologues exhibit doublets owing to the methyl group's internal rotation within the methanol molecule. Comprehensive computational analyses, including natural bond orbital (NBO) analysis, atoms in molecules (AIM) theory, and non-covalent interactions (NCI) index plots, reveal the coexistence of both O–H⋯π and C–H⋯O hydrogen bonds within the complex. Symmetry adapted perturbation theory with density functional theory (SAPT-DFT) calculations performed on the experimentally determined geometry provide an insight into the prominent role of electrostatic interactions in stabilising the overall structural arrangement.
Author(s): Gupta S, Cummings CN, Walker NR, Arunan E
Publication type: Article
Publication status: Published
Journal: Physical Chemistry: Chemical Physics
Year: 2024
Volume: 26
Issue: 29
Pages: 19795-19811
Online publication date: 04/07/2024
Acceptance date: 03/07/2024
Date deposited: 04/07/2024
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
URL: https://doi.org/10.1039/D4CP01916D
DOI: 10.1039/D4CP01916D
ePrints DOI: 10.57711/7acp-1634
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