Intra- and Intermolecular Second-Sphere Coordination Chemistry: Formation of Capsules, Half-Capsules, and Extended Structures with Hexaaquo- and Hexaamminemetal Ions

In the design of novel extended solids, particularly those based on weaker interactions, reliable “synthons” are a
valuable commodity. This work concerns the hydrogen-bonded assemblies which result from the second-sphere
coordination interactions between a highly preorganized trisulfonate ligand and hexaaquo metal ions. Significantly,
supramolecular structural variation, which may be rationalized on the basis of the features of the molecular building
blocks, is observed. The results are formation of second-sphere capsules with trivalent ions (Fe3+, Cr3+, Al3+), and
half-capsules with divalent ions (Mg2+, Zn2+). The divalent systems further assemble into extensively hydrogen-bonded hexagonal nets. Effects of geometrical variation of the building blocks are also observed when a Jahn−Teller-distorted divalent ion (Cu2+) is substituted for the perfectly octahedral species. The second-sphere effects on
the stabilization of the primary coordination sphere are illustrated by TGA experiments. In these assemblies, the
potential of a new supramolecular synthon is illustrated, that being the complementary cis-aquo sulfonate interaction.
These complexes illustrate the general utility of second-sphere effects, both as an assembly tool and to stabilize
metal complexes in the solid state. Finally, as a comparison, a hydrogen-bonded assembly with a hexaammine
complex of a trivalent metal (Co3+) is presented, which forms an extended network with a completely altered
hydrogen bonding array.