Johnson Solids: Anion-Templated Silver Thiolate Clusters Capped by Sulfonate.

Area of Science:

• Inorganic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• High-nuclearity metal clusters are of interest for their unique structural and electronic properties.
• Anion templating is a powerful strategy for constructing complex inorganic architectures.
• Silver(I) thiolates offer versatile coordination chemistry for cluster formation.

Purpose of the Study:

• To synthesize novel high-nuclearity silver(I) thiolate clusters using diverse anion templates.
• To elucidate the structures and assembly mechanisms of these clusters.
• To investigate their structural diversity, including discrete clusters and one-dimensional chains.

Main Methods:

• Single crystal X-ray diffraction for structural determination.
• Anion templating using S²⁻, SO₄²⁻, and various polyoxometalates (e.g., [Mo₅O₁₈]⁶⁻, [Mo₂O₈]⁴⁻, [Mo₄O₁₄(SO₄)]⁶⁻).
• Characterization of solution behavior and luminescent properties.

Main Results:

• Synthesis of six novel silver(I) thiolate clusters (SD/Ag1-SD/Ag6) with varying nuclearities.
• Structural diversity observed: discrete clusters ([S@Ag₆₀], [α-Mo₅O₁₈@Ag₃₆], [Mo₂O₈@Ag₃₀]₂, [Mo₄O₁₄(SO₄)@Ag₇₃]) and 1D chains ([SO₄@Ag₂₀] and [β-Mo₅O₁₈@Ag₃₆] based).
• Unique silver skeletons protected by thiolates and sulfonates, templated by internal anions.
• Silver shells exhibit Johnson solid polyhedral features.
• Largest cluster (SD/Ag6) doubly templated by [Mo₄O₁₄(SO₄)]⁶⁻.

Conclusions:

• Anion templating enables the construction of complex, high-nuclearity silver(I) thiolate clusters with diverse architectures.
• The synthesized clusters display unique structural motifs and geometries, including Johnson solids.
• The study expands the library of known silver cluster compounds and provides insights into their formation and properties.