Molecular cluster-based metal–organic frameworks (MOFs) are a class of crystalline solids. These compounds have applications in catalysis, sensors, and luminescence materials.

Thomas C. W. Mak and colleagues, Chinese University of Hong Kong, have synthesized a series of seven new crystalline complexes. The products include molecular silver-thiolate clusters and their covalently-linked frameworks. The team assembled the frameworks using the silver carbide precursor Ag₂C₂, in a process in which the C₂^2– ligand plays the role of a pre-template. This anion draws several Ag⁺ ions together to form C₂@Ag_n entities.

Several ellipsoidal tetradecanuclear silver thiolate molecular cluster compounds, such as Ag₁₄(S-iPr)₆(CO₂CF₃)₈·(DMSO)₆, were synthesized. The 3D MOF {Ag₃[Ag₁₄(S-iPr)₆(CO₂CF₃)₁₁(H₂O)₃CH₃OH]·(H₂O)_2.5}_n was also prepared. In addition, the disc-like anion-templated cluster CO₃@Ag_m(SR)₁₀ (R = isopropyl, cyclohexyl, or tert-butyl; m=18 or 20) was assembled into the chain-like {[HN(CH₃)₂CO]·[CO₃@Ag₁₈(S-tBu)₁₀(NO₃)₇(DMF)₄]·DMF}_n and the layered MOF {Ag[CO₃@Ag₂₀(S-iPr)₁₀(CO₂CF₃)₉(CO₂H CF₃)(CH₃OH₂)₂]}_n. This work is a basis for exploring the assembly of coinage-metal clusters containing various anionic ligands.

• Silver Thiolate Nano-sized Molecular Clusters and Their Supramolecular Covalent Frameworks: An Approach Toward Pre-templated Synthesis,
  Zi-Yi Chen, Dennis Y. S. Tam, Leon Li-Min Zhang, Thomas C. W. Mak,
  Chem. Asian J. 2017.
  DOI: 10.1002/asia.201701150