title: Supramolecular Covalence in Bifurcated Chalcogen Bonding.
abstract: 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.
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.|Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.
authors.forename: Pankaj Lochan
authors.identifier: http://orcid.org/0000-0003-0900-5214
authors.initials: PL
authors.lastname: Bora
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.|National Center for Biomolecular Research, Faculty of Science, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.
authors.forename: Martin
authors.identifier: http://orcid.org/0000-0001-5067-1994
authors.initials: M
authors.lastname: Novák
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.
authors.forename: Jan
authors.identifier: http://orcid.org/0000-0002-1203-9549
authors.initials: J
authors.lastname: Novotný
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.
authors.forename: Cina
authors.identifier: http://orcid.org/0000-0003-0755-8173
authors.initials: C
authors.lastname: Foroutan-Nejad
authors.affiliation: CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.|Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.|National Center for Biomolecular Research, Faculty of Science, Masaryk University, Kamenice 5, 62500, Brno, Czech Republic.
authors.forename: Radek
authors.identifier: http://orcid.org/0000-0002-3668-3523
authors.initials: R
authors.lastname: Marek
keywords: chalcogens; charge transfer; computational chemistry; halogen bonding; supramolecular chemistry