Chalcogen-Bonded [Se–N]2 Cyclic Supramolecular Synthons Enhanced by Halogen Bonds: Studies in the Gas Phase and Crystalline Phase

Chalcogen-bonded [Se-N]₂ is a strong cyclic supramolecular synthon in supramolecular chemistry. Selenadiazole is commonly used in the synthesis of [Se-N]₂. One nitrogen atom in a selenadiazole molecule participates in the formation of [Se-N]₂, while the other nitrogen atom can participate in the formation of other types of noncovalent bonds. Investigating the effect of neighboring noncovalent bonds on [Se-N]₂ is beneficial for its further synthesis and application. In this study, we combined theoretical calculations and crystallography to explore the effect of I···N halogen bonds on [Se-N]₂ in both the gas phase and the crystalline phase. Gas-phase calculations show that the formation of halogen bonds increases the strength of [Se-N]₂, and the strength of the halogen bond is directly proportional to the strength of [Se-N]₂. In the crystalline phase, [Se-N]₂ is influenced by more noncovalent bonds in addition to halogen bonds, making the results more complex. However, if the effect of other noncovalent bonds is relatively small, the strength of the halogen bond remains directly proportional to the strength of [Se-N]₂. It is believed that the conclusions drawn from halogen bonds are also applicable to other types of noncovalent bonds.