Chalcogen Bond Involving Zinc(II)/Cadmium(II) Carbonate and Its Enhancement by Spodium Bond

Abstract

Carbonate MCO3 (M = Zn, Cd) can act as both Lewis acid and base to engage in a spodium bond with nitrogen-containing bases (HCN, NHCH2, and NH3) and a chalcogen bond with SeHX (X = F, Cl, OH, OCH3, NH2, and NHCH3), respectively. There is also a weak hydrogen bond in the chalcogen-bonded dyads. Both chalcogen and hydrogen bonds become stronger in the order of F > Cl > OH > OCH3 > NH2 > NHCH3. The chalcogen-bonded dyads are stabilized by a combination of electrostatic and charge transfer interactions. The interaction energy of chalcogen-bonded dyad is less than −10 kcal/mol at most cases. Furthermore, the chalcogen bond can be strengthened through coexistence with a spodium bond in N-base-MCO3-SeHX. The enhancement of chalcogen bond is primarily attributed to the charge transfer interaction. Additionally, the spodium bond is also enhanced by the chalcogen bond although the corresponding enhancing effect is small.