COOPERATIVITY BETWEEN HYDROGEN BOND AND HALOGEN BOND INHBr⋯BrX⋯HBr (X = F, Cl, Br)

Abstract

An ab initio study has been carried out to investigate the structures, binding energies and atomic charge of the binary complexes HBrÁ Á Á BrX and ternary complexes HBrÁ Á Á BrXÁ Á Á HBr (X ¼ F, Cl, Br) at the MP2/aug-cc-pvdz theoretical level. Four types of interactions are observed among these systems: hydrogen bond, halogen bond, unusual hydrogen bond and unusual halogen bond. Two types of stable structures existed in the trimers: acyclic and monocyclic. The stabilities of the complexes may be decided by three factors: the strength of the halogen bond, the nature of halogen or hydrogen bond of intermolecular interaction and the type of the trimer's structure. The absolute value of the cooperativity contribution in these triads is in range of 0.77 $ 21.59%, which shows that the cooperative energy is of importance in them. The nature of the intermolecular interactions has been also investigated through the electrostatic potential and the theory of atoms in molecules (AIM). The values of r 2 at BCPs are positive in all complexes, indicating that the interactions are closed-shell. The ratio jVcj=G c of all complexes ranges from 0.782 to 0.935 (satisfy the condition jV c j=G c < 1) along with H c > 0, revealing that these complexes are predominantly electrostatic in character.

Computational Study on Metal-Ion-Decorated Prismane Molecules for Selective Adsorption of CO2 from Flue Gas Mixtures

“…The ratio of |V (r) |/G (r) for all the complexes is in the range between 0.77 and 0.93 and H (r) > 0 confirms the electrostatic nature of the interaction. 54,55 The binding energy calculations for metal ion−prismane complexes corroborate with the AIM results.…”

New equation for calculating total interaction energy in one noncyclic ABC triad and new insights into cooperativity of noncovalent bonds

“…Along with the interest in cooperativity in triads based on comparison of stabilization energies of triad and corresponding dyads the total interaction energy of a triad and pairwise interaction energies into its structure have been also studied using many‐body interaction energy (MBIE) approach . According to MBIE in an ABC triad the total interaction energy is given with following simplified equation: …”

Effect of Magnesium Bond on the Competition Between Hydrogen and Halogen Bonds and the Induction of Proton and Halogen Transfer

“…[32] It is thus not surprising that there has been some healthy study of cooperativity involving both HBs and XBs. [33][34][35][36][37][38][39][40][41][42][43] which suggested that under certain conditions, the presence of both of these interactions within a single system can reinforce one another. For example, aromatic triazole foldamers stabilized by intramolecular CH···O H-bonding can efficiently bind neutral tri-and bidentate organohalogens through multiple N···X (X=Cl, Br, and I) XBs.…”

“…For instance, assembly of molecules on surfaces can be steered by cooperative effects . It is thus not surprising that there has been some healthy study of cooperativity involving both HBs and XBs . which suggested that under certain conditions, the presence of both of these interactions within a single system can reinforce one another.…”