Evaluation of halide encapsulation in a cuboctahedron Cu12 cage. Structural and interaction energy in a highly coordinated cavity in the [{TpMo(μ3-S)4Cu3}4(μ12-X)]− (X = Cl−, Br−, I−) species

Abstract

Anion encapsulation is an attractive research field in supramolecular chemistry, given the crucial role of anion recognition in several issues. Here, we evaluate the nature of the anion encapsulation provided by the highly coordinating Cu₁₂-cuboctahedron cavity characterized in the [{TpMo(μ₃-S)₄Cu₃}₄(μ₁₂-I)]⁻ (1I) cluster. From calculations, the series of Cl-, Br-, and I- encapsulating species were evaluated, highlighting the flexibility of the metallic cage to maximize the interaction with a main electrostatic interaction character complemented with a sizable charge transfer. Thus, using inorganic cages featuring multiple binding sites offers a versatile template for further artificial receptors for anions and other species.