Unconventional Radical and Radical-Hole Site-Based Interactions in Halogen-Bearing Dimers and Trimers: A Comparative Study

Funding Sponsor

King Saud University

Fifth Author's Department

Chemistry Department

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https://doi.org/10.1021/acsomega.4c04620

All Authors

Mahmoud A.A. Ibrahim, Heba S.M. Abd Elhafez, Mohammed N.I. Shehata, Nayra A.M. Moussa, Shaban R.M. Sayed, Mahmoud E.S. Soliman, Muhammad Naeem Ahmed, Mohamed Khaled Abd El-Rahman, Tamer Shoeib

Document Type

Research Article

Publication Title

ACS Omega

Publication Date

9-17-2024

doi

10.1021/acsomega.4c04620

Abstract

Radical (R•) and R•-hole site-based interactions are comparatively studied, for the first time, using ab initio methods. In this regard, R•-bearing molecules •XO3 (where X = Cl, Br, and I) were subjected to direct interaction with NH3 within dimeric and trimeric forms in the form of NH3···•XO3/•XO3···NH3 and NH3···•XO3···NH3 complexes, respectively. As confirmed by electrostatic potential analysis, the studied R•-bearing molecules •XO3 had the outstanding potentiality to interact as Lewis acid centers via two positive sites dubbed as R• and R•-hole sites. Such an observation proposed the potentiality of the considered •XO3 molecules to engage in unconventional R• and well-established R•-hole site-based interactions with Lewis bases. This was confirmed by negative interaction (Eint) energies, ranging from −4.93 to −19.89 kcal/mol, with higher favorability for R• site-based interactions over the R•-hole site-based ones. MP2 energetic features furnished higher preferability for the R• site-based interactions than the R•-hole site-based ones in the case of chlorine- and bromine-bearing complexes, and the reverse was true for the iodine-bearing complexes. Moreover, elevated Eint values were recorded for the NH3···•XO3···NH3 trimers over the NH3···•XO3 and •XO3···NH3 dimers, outlining the higher preference of the •XO3 molecules to engage in R• and R•-hole site-based interactions in the trimeric form over the dimeric one. These results might be considered a requisite linchpin for numerous forthcoming supramolecular chemistry and crystal engineering studies.

First Page

38743

Last Page

38752

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