Tetrel Bonding in Anion Recognition: A First-Principles Investigation

TL;DR

This study uses advanced computational methods to analyze tetrel bonding in 25 molecule-anion complexes, revealing the strength, nature, and variability of these interactions and their dependence on the tetrel atom involved.

Contribution

It provides a comprehensive first-principles investigation of tetrel bonds in anion recognition, highlighting the differences in interaction energies and bonding characteristics across various tetrel atoms.

Findings

Tetrel bonds vary from weak to very strong depending on the atom and complex.

High-level calculations show significant interaction energy variation among complexes.

Charge density analysis reveals the nature of chemical bonding in these complexes.

Abstract

Twenty-five molecule-anion complex systems [I4Tt...X-] (Tt = C, Si, Ge, Sn and Pb; X = F, Cl, Br, I, At) were examined using density functional theory (wB97XD) and ab initio (MP2 and CCSD) methods to demonstrate the ability of the tetrel atoms in molecular entities, I4Tt, to recognize the halide anions when in close proximity. The tetrel bond strength for the [I4C...X-] series, and [I4Tt...X-] (Tt = Si, Sn; X = I, At), was weak-to-moderate, whereas that in the remaining 16 complexes was dative tetrel bond type with very large interaction energies and short Tt...X close contact distances. The basis set superposition error corrected interaction energies calculated with the highest-level theory applied, [CCSD(T)/def2-TZVPPD], ranged from -3.0 to -112.2 kcal mol-1. The significant variation in interaction energies was realized as a result of different levels of tetrel bonding environment between the interacting partners at the equilibrium geometries of the complex systems. Although the wB97XD computed intermolecular geometries and interaction energies of [I4Tt...X-] were close to those predicted by the highest level of theory, the MP2 results were shown to be misleading for some of the molecule-anion complex systems investigated. To provide insight into the nature of the intermolecular chemical bonding environment in the 25 molecule-anion complexes investigated, we discussed the charge density based topological and isosurface features that emanated from the application of quantum theory of atoms in molecules and independent gradient model approaches, respectively.