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Characterization of chalcogen bonding interactions via an in‐depth conceptual quantum chemical analysis
Author(s) -
De Vleeschouwer Freija,
Denayer Mats,
Pinter Balazs,
Geerlings Paul,
De Proft Frank
Publication year - 2018
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25099
Subject(s) - hsab theory , chalcogen , natural bond orbital , fukui function , chemistry , density functional theory , computational chemistry , electron density , non covalent interactions , atoms in molecules , quantum chemistry , valence electron , chemical physics , chemical bond , lewis acids and bases , crystallography , molecule , electron , hydrogen bond , quantum mechanics , organic chemistry , physics , supramolecular chemistry , electrophile , catalysis
The chalcogen bond has been acknowledged as an influential noncovalent interaction (NCI) between an electron‐deficient chalcogen (donor) and a Lewis base (acceptor). This work explores the main features of chalcogen bonding through a large‐scale computational study on a series of donors and acceptors spanning a wide range in strength and character of this type of bond: (benzo)chalcogenadiazoles (with Ch = Te/Se/S) versus halides and neutral Lewis bases with O, N, and C as donor atoms. We start from Pearson's hard and soft acids and bases (HSAB) principle, where the hard nature of the chalcogen bond is quantified through the molecular electrostatic potential and the soft nature through the Fukui function. The σ‐holes are more pronounced when going down in the periodic table and their directionality matches the structural orientation of donors and acceptors in the complexes. The Fukui functions point toward an n→σ*‐type interaction. The initial conjectures are further scrutinized using quantum mechanical methods, mostly relating to the systems' electron density. A Ziegler–Rauk energy decomposition analysis shows that electrostatics plays a distinctly larger role for the soft halides than for the hard, uncharged acceptors, associated with the softness matching within the HSAB principle. The natural orbital for chemical valence analysis confirms the n→σ* electron donation mechanism. Finally, the electron density and local density energy at the bond critical point in the quantum theory of atoms in molecules study and the position of the spikes in the reduced density gradient versus density plot in the NCI theory situate the chalcogen bond in the same range as strong hydrogen bonds. © 2017 Wiley Periodicals, Inc.