Cooperative effects between F … Ag bonded and X … Br (Cl) halogen-bonded interaction in BrF(ClF) … AgX … BrF(ClF) (X = F, Cl, Br) complexes: a theoretical study

Abstract

The equilibrium structures, interaction energies and binding properties of ternary BrF(ClF) …  AgX … BrF(ClF)(X = F, Cl, Br) complexes and the corresponding binary systems have been studied by DFT method at the X3LYP/aug-cc-pVQZ level. Cooperative effects are probed by analysing charge transfer, electronic properties and orbital interactions when F … Ag bond and X … Br (Cl) halogen bond coexist in the same complex. The results indicate that the X … Br (Cl) halogen bond has a greater enhancing effect than the F … Ag bond does, resulting in a shorter binding distances, larger interaction energies and greater electron densities for the ternary complexes than for the corresponding binary ones. In addition, the origins of both the F … Ag bond and X … Br (Cl) halogen bond have been deduced via energy decomposition.

GRAPHICAL ABSTRACT

KEYWORDS:

• Cooperative effects
• electron density
• halogen bonds
• molecular electrostatic potential
• orbital interaction
• energy decomposition

Additional information

Funding

This work was supported by Hunan Provincial Natural Science Foundation of China [Grant Number 2017JJ2095]; the Scientific Research Fund of Hunan Provincial Education Department [Grant Number 16C0625]; the National Natural Science Foundation of China [Grant Number 21401055].