Effect of External Electric Field on Tetrel Bonding Interactions in (FTF₃···FH) Complexes (T = C, Si, Ge, and Sn)

Abstract

A quantum chemical study was accomplished on the σ-hole interactions of the barely explored group IV elements, for the first time, in the absence and presence of the positively and negatively directed external electric field (EEF). The analyses of molecular electrostatic potential addressed the occurrence of the σ-hole on all the inspected tetrel atoms, confirming their salient versatility to engage in σ-hole interactions. MP2 energetic findings disclosed the occurrence of favorable σ-hole interactions within the tetrel bonding complexes. The tetrel bonding interactions became stronger in the order of C < Si < Ge < Sn for F–T–F3···FH complexes with the largest interaction energy amounting to −19.43 kcal/mol for the optimized F–Sn–F3···FH complex under the influence of +0.020 au EEF. The interaction energy conspicuously evolved by boosting the magnitude of the positively directed EEF value and declining the negatively directed EEF one. The decomposition analysis for the interaction energies was also executed in terms of symmetry-adapted perturbation theory, illuminating the dominant electrostatic contribution to all the studied complexes’ interactions except carbon-based interactions controlled by dispersion forces. The outcomes that emerged from the current work reported significantly how the direction and strength of the EEF affect the tetrel-bonding interactions, leading to further improvements in the forthcoming studies of supramolecular chemistry and materials science.

Effects of Lewis Basicity and Acidity on σ-Hole Interactions in Carbon-Bearing Complexes: A Comparative Ab Initio Study

“…From QTAIM diagrams demonstrated in Figure 5 , three BPs and BCPs were denoted within the Set I and II complexes, highlighting the eminent contributions of the three coplanar halogens within the considered interactions that were in great agreement with previous studies [ 63 ]. The same observations were found for the F-C-F 3 ∙∙∙NCX and W-C-F 3 /F-C-X 3 ∙∙∙NCF complexes ( Figure S3 ).…”

“…Using PoC approach, the effect of N∙∙∙ and C∙∙∙PoC distances were examined for the considered the NC-C 6 H 2 -X 3 /NCX (LB)∙∙∙ and W-C-F 3 ∙∙∙/F-C-X 3 (LA)∙∙∙PoC systems under the effect of PoC = ±0.50 au in distance range of 2.5–5.5 Å along the x -axis with a 0.1 Å step size. The molecular stabilization energies ( E stabilization ) were then evaluated and given from Equation (1) [ 63 , 72 , 73 ]: …”

Definition of the tetrel bond

“…o. the tetrel bond strength typically increases with a given TtBA A, as the electronegativity of Tt decreases in the order C > Si > Ge > Sn > Pb and the electron withdrawing ability of R increases; 13,19,39,68 there may be an exception when the chemical environment alters the nature of the reactivity between the TtB donor and acceptor moieties. 27…”

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

“…The σ-hole interactions are of growing interest to researchers from various disciplines, owing to their wide applications in catalysis [ 1 ], anion recognition [ 2 ], biological systems [ 3 , 4 ], crystal materials [ 5 , 6 ], and drug discovery [ 7 ]. The occurrence of such interactions was mainly ascribed to the anisotropic distribution of the electron density on the surfaces of group IV-VII elements [ 8 , 9 , 10 , 11 , 12 , 13 ], resulting in the emergence of an electron depletion region coined as “σ-hole” [ 14 , 15 ]. Among σ-hole interactions, the halogen bond encouraged growing attention by dint of its decisive character in protein–ligand binding affinity [ 16 , 17 , 18 ], crystal engineering [ 19 , 20 , 21 ], and organo-catalysis [ 22 , 23 ].…”