Cubic box versus spheroidal capsule built from defect and intact pentagonal units.

Area of Science:

• Inorganic Chemistry
• Materials Science
• Nanotechnology

Background:

• Polyoxothiomolybdates are complex inorganic clusters with diverse structures and properties.
• High-nuclearity clusters offer unique opportunities for designing novel molecular architectures.
• Understanding the structure-property relationships in these materials is crucial for their applications.

Purpose of the Study:

• To synthesize and characterize a novel high-nuclearity polyoxothiomolybdate.
• To investigate the solid-state structure and properties of the new compound.
• To explore the potential functionalizability of the synthesized molecular system.

Main Methods:

• Single-crystal X-ray crystallography for structural determination.
• Spectroscopic characterization including (1)H NMR, IR, Raman, and UV-vis spectroscopy.
• Analysis of the crystal structure to identify key features like voids and accessible sites.

Main Results:

• Successful preparation and characterization of the high-nuclearity polyoxothiomolybdate [H(8)Mo(84)S(48)O(188)(H(2)O)(12)(CH(3)COO)(24)](32-).
• Discovery of an unprecedented nanoscaled anionic cubic structure ({Mo(84)}-type).
• Identification of a large internal void (approx. 9 Å diameter) accessible through six square faces and 24 exchangeable acetate ligands, indicating high functionalizability.

Conclusions:

• The synthesized {Mo(84)}-type polyoxothiomolybdate represents a novel molecular architecture with a unique cubic structure.
• The open framework and accessible void suggest potential applications in areas like host-guest chemistry or catalysis.
• The presence of exchangeable acetate ligands makes this molecular system a promising platform for further functionalization and material design.