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On the Interplay between Charge‐Shift Bonding and Halogen Bonding
Author(s) -
Sarr Serigne,
Graton Jérôme,
Montavon Gilles,
Pilmé Julien,
Galland Nicolas
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201901023
Subject(s) - halogen bond , halogen , polarizability , chemistry , atom (system on chip) , charge (physics) , halide , computational chemistry , chemical physics , crystallography , molecule , inorganic chemistry , physics , organic chemistry , quantum mechanics , alkyl , computer science , embedded system
Abstract The nature of halogen‐bond interactions has been analysed from the perspective of the astatine element, which is potentially the strongest halogen‐bond donor. Relativistic quantum calculations on complexes formed between halide anions and a series of Y 3 C−X (Y=F to X, X=I, At) halogen‐bond donors disclosed unexpected trends, e. g ., At 3 C−At revealing a weaker donating ability than I 3 C−I despite a stronger polarizability. All the observed peculiarities have their origin in a specific component of C−Y bonds: the charge‐shift bonding. Descriptors of the Quantum Chemical Topology show that the halogen‐bond strength can be quantitatively anticipated from the magnitude of charge‐shift bonding operating in Y 3 C−X. The charge‐shift mechanism weakens the ability of the halogen atom X to engage in halogen bonds. This outcome provides rationales for outlier halogen‐bond complexes, which are at variance with the consensus that the halogen‐bond strength scales with the polarizability of the halogen atom.