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

Na Liu,Xiaoying Xie,Qingzhong Li

doi:10.3390/molecules26216443

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.

Highlights

Chalcogen Bond InvolvingZinc and cadmium are two of the most widely used non-ferrous metals because of their unique physical and chemical properties [1]
MCO3 has been accepted as a promising material for optical devices in the ultraviolet region due to its fascinating crystal structure, high birefringence, nonlinear optical properties, and transparency [5,6,7]
We explore the chalcogen bond formed by carbonate MCO3 (M = Zn, Cd) with SeHX (X = F, Cl, OH, OCH3, NH2, and NHCH3 ) to unveil the substituent effect on the strength of chalcogen bond and its origin

Summary

Introduction

Zinc and cadmium are two of the most widely used non-ferrous metals because of their unique physical and chemical properties [1] They have been explored mainly in natural minerals in the form of carbonates. MCO3 has been accepted as a promising material for optical devices in the ultraviolet region due to its fascinating crystal structure, high birefringence, nonlinear optical properties, and transparency [5,6,7] Owing to their special electronic energy band structures, these carbonates have drawn extensive attention in the fields of chemical sensing, luminescence, lithium ion battery anode materials, catalysis, and magnetic materials [8,9,10].

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