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Halogen Bonding Propensity in Solution: Direct Observation and Computational Prediction.
Bramlett, Taylor A; Matzger, Adam J.
Afiliação
  • Bramlett TA; Department of Chemistry, University of Michigan, 930 North University Ave, Ann Arbor, MI, 48109, USA.
  • Matzger AJ; Department of Chemistry, University of Michigan, 930 North University Ave, Ann Arbor, MI, 48109, USA.
Chemistry ; 27(62): 15472-15478, 2021 Nov 05.
Article em En | MEDLINE | ID: mdl-34546600
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.
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Texto completo: 1 Base de dados: MEDLINE Assunto principal: Halogênios Tipo de estudo: Prognostic_studies / Risk_factors_studies Idioma: En Revista: Chemistry Ano de publicação: 2021 Tipo de documento: Article

Texto completo: 1 Base de dados: MEDLINE Assunto principal: Halogênios Tipo de estudo: Prognostic_studies / Risk_factors_studies Idioma: En Revista: Chemistry Ano de publicação: 2021 Tipo de documento: Article