Influence of Anions in Silver Supramolecular Frameworks: Structural Characteristics and Sorption Properties.

The complexation of a preorganized thioether-functionalized
bis­(pyrazolyl)­methane ligand (L) with silver precursors produces supramolecular
structures organized at two hierarchical levels: [AgL]6(X)6 metal–organic cyclic hexamers and their organization
in 3D architectures. The cyclic toroidal hexamers of 22–26
Å external diameter are found to be stable already in solution
before self-assembly into the crystalline state. In the 3D lattice,
the hexameric building block are arranged in different highly symmetric
space groups as a function of a variety of anions (cubic Fd3̅ with PF6– or BF4– and rhombohedral R3̅ with
CF3SO3– or NO3–) and form cavities with the geometrical shapes of
Platonic solids (tetrahedron and octahedron) that can be occupied
by a variety of solvent molecules. Upon evacuation, cubic crystals
can produce stable frameworks with permanent porosity, which can absorb
reversibly several vapors, CO2 and CH4.