Chalcogen ‘like-like’ Interactions Involving Trisulphide and Triselenide Compounds: A Combined CSD and Ab Initio Study

Antonio Bauzá,Antonio Frontera

doi:10.3390/molecules23030699

Antonio Bauzá, Antonio Frontera

Open Access

https://doi.org/10.3390/molecules23030699

Copy DOI

Abstract

In this manuscript, we combined a search in the Cambridge Structural Database (CSD) and ab initio calculations (RI-MP2/def2-TZVPD level of theory) to analyze the ability of trisulphide and triselenide moieties to establish chalcogen ‘like-like’ interactions. A preliminary CSD inspection revealed two predominant structural patterns, depending on the anti or syn conformation adopted by the substituents of the S3/Se3 bridge, leading to bifurcated or double chalcogen bonding interactions, respectively. In order to analyze these two relevant structural motifs we have used a series of S and Se derivatives Ch3X2 (Ch = S and Se and X = H, F, CN, and CF3) which act as both electron donor (using the lone pairs) and acceptor (using the σ-holes) entities. Besides, we have carried out “atoms in molecules” (AIM) and natural bonding orbital (NBO) analyses to further describe and characterize the chalcogen bonding interactions described herein. As far as we know, chalcogen···chalcogen interactions involving trichalconides (S3/Se3) have not been previously described in literature a may be of great importance in the preparation and characterization of new solids based on this subclass of σ-hole bonding.

Highlights

The conjunction of a great deal of noncovalent forces is considered of great importance for the advance and progress in the field of Supramolecular chemistry [1,2]
A depth comprehension of them is vital for chemists working in this discipline, since many chemical and biological processes are governed by an intricate combination of noncovalent interactions, settling the basis of highly specific recognition processes
The geometries of the complexes studied have been fully optimized at the RI-MP2/def2The geometries of the complexes studied have been fully optimized at the TZVPD level of theory

Summary

Introduction

The conjunction of a great deal of noncovalent forces is considered of great importance for the advance and progress in the field of Supramolecular chemistry [1,2]. Interactions between hosts and guests cover the formation of novel supramolecular assemblies presenting high affinities even in highly competitive media [3,4,5,6]. For this reason, a proper description and understanding of noncovalent interactions between molecules is key for success in this field of research. One of the classical and well-known supramolecular forces present in many chemical and biological environments is hydrogen bonding [7]. A series of studies using the Cambridge Structural Database (CSD)

Methods

Results

Conclusion