Silver Thiolate Clusters and Supramolecular Covalent Frameworks

Silver Thiolate Clusters and Supramolecular Covalent Frameworks

Author: Andrei Dragan

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 C22– ligand plays the role of a pre-template. This anion draws several Ag+ ions together to form C2@Agn 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@Agm(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.


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