Computer Modeling of Halogen Bonds and Other σ-Hole Interactions

Abstract

In the field of noncovalent interactions a new paradigm has recently become popular. It stems from the analysis of molecular electrostatic potentials and introduces a label, which has recently attracted enormous attention. The label is σ-hole, and it was first used in connection with halogens. It initiated a renaissance of interest in halogenated compounds, and later on, when found also on other groups of atoms (chalcogens, pnicogens, tetrels and aerogens), it resulted in a new direction of research of intermolecular interactions. In this review, we summarize advances from about the last 10 years in understanding those interactions related to σ-hole. We pay particular attention to theoretical and computational techniques, which play a crucial role in the field.

It Is Important to Compute Intramolecular Hydrogen Bonding in Drug Design?

“…Several works have been carried out regarding the tunability of the mentioned σ -holes in different types of interactions, including halogen, chalcogen, and pnicogen [438,439,440,441]. In particular, the effect on the σ -hole upon substitution on aromatic rings has been previously studied [438,442,443,444].…”

Isomorphous Crystals from Diynes and Bromodiynes Involved in Hydrogen and Halogen Bonds

“…In order to gain more insight into the energetics at stake in the crystals of 1 and 2, a DFT study was carried out on simplified models 8-8-9 and 8-8-10 of these crystals ( Figure 5) [68][69][70][71].…”

“…In order to gain more insight into the energetics at stake in the crystals of 1 and 2, a DFT study was carried out on simplified models 8-8-9 and 8-8-10 of these crystals ( Figure 5) [68][69][70][71]. Two DFT methods were applied to study these systems, namely the widely used B3LYP functional as well as the M06-2X method known to be more suitable to treat weak interactions and peptides [74,75].…”

Photo-Induced Atom-Transfer Radical Reactions Using Charge–Transfer Complex between Iodine and Tertiary Amine

“…Charge-Transfer Complex between Amine and Iodine on halogen bonding interactions have been a subject of current interest. 30,31) To understand the above results, we calculated the optimized structures of iodine complexes. The calculation shows that the noncovalent interaction between trimethylamine and I 2 is strong to form the stable CT complex, while pyridine weakly interacts with I 2 .…”