4 years ago

Supramolecular Covalence in Bifurcated Chalcogen Bonding

Supramolecular Covalence in Bifurcated Chalcogen Bonding
Radek Marek, Pankaj Lochan Bora, Cina Foroutan-Nejad, Jan Novotný, Martin Novák
Supramolecular interactions are generally classified as noncovalent. However, recent studies have demonstrated that many of these interactions are stabilized by a significant covalent component. Herein, for systems of the general structure [MX6]2−:YX2 (M=Se or Pt; Y=S, Se, or Te; X=F, Cl, Br, I), featuring bifurcated chalcogen bonding, it is shown that, although electrostatic parameters are useful for estimating the long-range electrostatic component of the interaction, they fail to predict the correct order of binding energies in a series of compounds. Instead, the Lewis basicity of the individual substituents X on the chalcogen atom governs the trends in the binding energies through fine-tuning the covalent character of the chalcogen bond. The effects of substituents on the binding energy and supramolecular electron sharing are consistently identified by an arsenal of theoretical methods, ranging from approaches based on the quantum chemical topology to analytical tools based on the localized molecular orbitals. The chalcogen bonding investigated herein is driven by orbital interactions with significant electron sharing; this can be designated as supramolecular covalence. Let's share! Supramolecular covalence, quantified by orbital interactions and interatomic electron sharing, is demonstrated to dominate the chalcogen-bond interaction. Electrostatic potentials fail to predict the trends in binding energies (see figure).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700179

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