Work

Deriving General Energy Predictors for Pnictogen Bonding

Year: 2026

Type: article

Abstract: PnX, where Pn represents nitrogen through bismuth and X represents chlorine, bromine, or iodine, acting as σ-hole donors with a diverse set of up to twenty-one different nitrogen- and oxygen-based Lewis bases. All complexes were investigated at the PBE0-D3/def2-TZVP level of theory. For every complex, a topological analysis according to Bader's quantum theory of atoms in molecules (QTAIM) was performed to correlate the interaction energies with the potential energy density values at the bond critical points. We established a linear correlation with reasonable R-squared values for the coordination behavior of each pnictogen atom. Furthermore, the results demonstrate that, as the size, polarizability, and σ-hole intensity of the pnictogen atom increase, the likelihood of forming additional secondary noncovalent interactions also rises. Consequently, a clear differentiation must be made between pure pnictogen bonding and a combination of pnictogen bonding with secondary interactions. This distinction is supported by the analysis of several published crystal structures. We propose general energy predictors for the determination of pure pnictogen bond energies.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.71386

Authors: Jan Langwald, Antonio Frontera

Institutions: University of Cologne, Universitat de les Illes Balears

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,640

Funder: Ministerio de Ciencia, Innovación y Universidades