Heterometallic gold(I)-thallium(I) compounds with crown thioethers

Area of Science:

• Coordination Chemistry
• Supramolecular Chemistry
• Materials Science

Background:

• Polymeric gold-thallium compounds with aryl ligands are known.
• Crown thioethers are versatile ligands in coordination chemistry.
• Metal-metal interactions in gold and thallium complexes can lead to interesting photophysical properties.

Purpose of the Study:

• To synthesize and characterize novel polymeric gold-thallium complexes with crown thioethers.
• To investigate the structural and photophysical properties of these new compounds.
• To understand the role of metal-metal interactions in their luminescence.

Main Methods:

• Reaction of polymeric [{Au(C6X5)2}Tl]n (X = Cl, F) with crown thioethers ([9]aneS3, [14]aneS4, [24]aneS8).
• X-ray diffraction studies to determine the solid-state structures.
• Photoluminescence spectroscopy to study optical properties in solid-state and solution.
• Density Functional Theory (DFT) calculations to elucidate electronic transitions.

Main Results:

• Synthesis of novel gold-thallium complexes with crown thioethers, including polymeric and tetranuclear structures.
• X-ray diffraction confirmed structures formed via Tl-S bonds and Au-Tl/Au-Au contacts.
• All synthesized complexes displayed luminescence in the solid state, which was absent in solution.
• DFT calculations provided insights into the electronic transitions responsible for luminescence.

Conclusions:

• The synthesized gold-thallium-crown thioether complexes exhibit unique structural motifs and solid-state luminescence.
• Luminescence is strongly dependent on the presence of metal-metal interactions, which are sensitive to the phase (solid vs. solution).
• These findings contribute to understanding structure-property relationships in polynuclear metal complexes.