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

Abstract

Soft molecular host frameworks made of the hydrogen-bonded metal complex (MC) Co(NH3)(6)3+ 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.

Synthesis and Structural Studies of Three‐Dimensional Supramolecular Motifs Derived from Neutral and Cationic Zinc Alkanesulfonates

“…The cumulative effects of secondary interactions are pivotal to the stability of higher‐dimensional structures, and these interactions provide flexibility to porous frameworks. The synthetic approach often requires the involvement of zero‐, one‐, or two‐dimensional coordination frameworks associated with complementary ligands that offer secondary interactions . Several such reliable synthons that encode well‐defined noncovalent motifs have been reported.…”

Charge-Assisted Hydrogen-Bonded Networks of NH4+ and [Co(NH3)6]3+ with the New Linker Anion of 4-Phosphono-Biphenyl-4′-Carboxylic Acid

“…In a similar approach, 4-phosphono benzoic acid was crystallized with hexaaquacobalt(II) [43], and sulfonate ligands were crystallized with [Co(NH 3 ) 6 ] 3+ cations, resulting in hydrogen-bonded networks [44].…”

Hydrothermal synthesis, crystal structures and properties of Tiron-bridged di- and trinuclear strontium complexes containing nitrogen-donor ligands

“…The diverse architectures involving sulfonates have been reported with alkali, alkaline-earth, d-block, and 4f metal cations [13][14][15][16][17]. In addition, the sulfonate groups and hydrogen donors easily connect through hydrogen bonding, which can further cross-link into a higher dimensional and more stabilized structures [18][19][20].…”