Hydrogen-Bonded Metal-Complex Sulfonate (MCS) Inclusion Compounds: Effect of the Guest Molecule on the Host Framework

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Abstract
Soft molecular host frameworks made of the hydrogen-bonded metal complex (MC) Co(NH3)63+ and 4,4‘-biphenyldisulfonate (BPDS) include different guest molecules to form inclusion compounds of the type (MC)2(BPDS)3·n(guest). Structurally characterized were six compounds with guest molecules of DMSO, DMF, piperidine, acetone, acetonitrile, and THF. The metal-complex sulfonate frameworks in all of them are of the pillared layer type where the layers are constructed of extensively hydrogen-bonded metal-complex cations and sulfonate (S) anions (and some hydrogen-bonded water) while the organic residues of the 4,4‘-biphenyldisulfonate serve as pillars. The hydrogen-bonded MCS layers and the orientations of the pillars adjust and rearrange in order to generate cavities that would accommodate different guest molecules. The steric, electronic, and hydrogen-bonding needs of the guest molecules mold the soft framework into different structures. These MCS host−guest frameworks are very close structural analogues of the well-studied guanidinium sulfonate (GS) networks and mimic their flexibility and overall durability.