Designing Intermolecular Interactions between Halogenated Peripheries of Inorganic and Organic Molecules: Electrostatically Directed MX⋅⋅⋅X′C Halogen Bonds

Abstract

Complementary electronic properties of inorganic and organic halogen species are exploited in the design of molecular networks that employ MX⋅⋅⋅X′C halogen bonds. The dominance of electrostatic effects in this type of interaction over other energy terms, such as charge transfer, is demonstrated by the study of a series of eight isostructural compounds (4-X′pyH)2[CoX4] (see picture; X=Cl, Cl/Br, Br, I; X′=Cl, Br).