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Halogen Bonding Propensity in Solution: Direct Observation and Computational Prediction.

Authors :
Bramlett, Taylor A.
Matzger, Adam J.
Source :
Chemistry - A European Journal. 11/5/2021, Vol. 27 Issue 62, p15472-15478. 7p.
Publication Year :
2021

Abstract

Halogen‐bonded complexes are often designed by consideration of electrostatic potential (ESP) predictions. ESP predictions do not capture the myriad variables associated with halogen bond (XB) donors and acceptors; thus, binding interaction cannot be quantitatively predicted. Here, a discrepancy between predictions based on ESP energy difference (ΔVs) and computed gas phase binding energy (ΔEbind) motivated the experimental determination of the relative strength of halogen bonding interactions in solution by Raman spectroscopic observation of complexes formed from interacting five iodobenzene‐derived XB donors and four pyridine XB acceptors. Evaluation of ΔEbind coupled with absolutely‐localized molecular orbital energy decomposition analysis (ALMO‐EDA) deconvolutes halogen bonding energy contributions and reveals a prominent role for charge transfer (CT) interactions. Raman spectra reveal ΔEbind accurately predicts stronger interactions within iodopentafluorobenzene (IPFB) complexes than with 1‐iodo‐3,5‐dinitrobenzene (IDNB) complexes even though IPFB has similar electrostatics to IDNB and contains a smaller σ‐hole. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
09476539
Volume :
27
Issue :
62
Database :
Academic Search Index
Journal :
Chemistry - A European Journal
Publication Type :
Academic Journal
Accession number :
153435174
Full Text :
https://doi.org/10.1002/chem.202102522