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On the Interplay between Charge‐Shift Bonding and Halogen Bonding

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 Y3C-X (Y = F to X, X = I, At) halogen-bond donors disclosed unexpected trends, e.g., At3C-At revealing a weaker donating ability than I3C-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 Y3C-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.
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Serigne Sarr, Jérôme Graton, Gilles Montavon, Julien Pilmé, Nicolas Galland. On the Interplay between Charge‐Shift Bonding and Halogen Bonding. ChemPhysChem, Wiley-VCH Verlag, 2020, ⟨10.1002/cphc.201901023⟩. ⟨hal-02444757⟩

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