Fluoride Anions: Unexploited but Effective Halogen Bond Acceptors

Andrea Daolio; Andrea Pizzi; Susanta K Nayak; Justyna Dominikowska; Giancarlo Terraneo; Pierangelo Metrangolo; Giuseppe Resnati

doi:10.1002/asia.202300520

Fluoride Anions: Unexploited but Effective Halogen Bond Acceptors

Chem Asian J. 2023 Sep 1;18(17):e202300520. doi: 10.1002/asia.202300520. Epub 2023 Jul 20.

Authors

Andrea Daolio¹, Andrea Pizzi¹, Susanta K Nayak², Justyna Dominikowska³, Giancarlo Terraneo¹, Pierangelo Metrangolo¹, Giuseppe Resnati¹

Affiliations

¹ NFMLab, Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano via, L. Mancinelli 7, I-20131, Milano, Italy.
² Department of Chemistry, Visvesvaraya National Institute of Technology, S. Ambazari Rd., Nagpur, 440 010, Maharashtra, India.
³ Department of Physical Chemistry, University of Lodz, Pomorska Łódź, 163/165, 90-236, Lodz, Poland.

PMID: 37471203
DOI: 10.1002/asia.202300520

Abstract

Due to their high electron density, fluoride anions can be considered the most effective halogen bond (HaB) acceptors among the halides. However, under common experimental conditions, F^- uncommonly acts as HaB acceptor, expectedly as it is present in hydrated form. Herein we report that under specific crystallization conditions a hydrogen bond-free F^- functioning as donor of electron density can be obtained, with the formed HaBs constituting the driving force of the observed crystal packings. Computations confirm the strength of these HaBs compared to analogous interactions involving other halides.

Keywords: Anhydrous fluoride; Fluoride anion; Halide anions; Halogen Bond; Halogen Bond acceptor.

Abstract

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