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Molecules 2018, 23(1), 18; https://doi.org/10.3390/molecules23010018

Substituent Effects in Multivalent Halogen Bonding Complexes: A Combined Theoretical and Crystallographic Study

Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), Spain
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Received: 13 November 2017 / Revised: 18 December 2017 / Accepted: 20 December 2017 / Published: 22 December 2017
(This article belongs to the Special Issue Halogen Bonds and Beyond)
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Abstract

In this manuscript, we combined ab initio calculations (RI-MP2/def2-TZVPD level of theory) and a search in the CSD (Cambridge Structural Database) to analyze the influence of aromatic substitution in charge-assisted multivalent halogen bonding complexes. We used a series of benzene substituted iodine derivatives C6H4(IF4)Y (Y = H, NH2, OCH3, F, CN, and CF3) as Lewis acids and used Cl as electron rich interacting atoms. We have represented the Hammett’s plot and observed a good regression coefficient (interaction energies vs. Hammett’s σ parameter). Additionally, we demonstrated the direct correlation between the Hammett’s σ parameter and the value of molecular electrostatic potential measured at the I atom on the extension of the C–I bond. Furthermore, we have carried out AIM (atoms in molecules) and NBO (natural bonding orbital) analyses to further describe and characterize the interactions described herein. Finally, we have carried out a search in the CSD (Cambridge Structural Database) and found several X-ray structures where these interactions are present, thus giving reliability to the results derived from the calculations. View Full-Text
Keywords: multivalent halogen bonding interactions; CSD search; RI-MP2 calculations; AIM and NBO analyses multivalent halogen bonding interactions; CSD search; RI-MP2 calculations; AIM and NBO analyses
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Bauzá, A.; Quiñonero, D.; Frontera, A. Substituent Effects in Multivalent Halogen Bonding Complexes: A Combined Theoretical and Crystallographic Study. Molecules 2018, 23, 18.

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