[Au(S-C₆F₅)] and [Au(S-C₆F₄-CF₃)]: Reactivity, Structure, DSC, and Calculation Studies

Area of Science:

• Inorganic Chemistry
• Materials Science
• Coordination Chemistry

Background:

• Gold(I) complexes are of interest due to their unique electronic and structural properties.
• Fluorinated organic ligands can impart distinct characteristics to metal complexes.
• Coordination polymers offer tunable structures and potential applications.

Purpose of the Study:

• To synthesize and characterize novel gold(I) coordination polymers using fluorinated aryl thiolates.
• To investigate the structural transformation of these polymers upon reaction with pyridine and DMSO.
• To explore the nature of intermolecular interactions, specifically Au···Au interactions, in the resulting complexes.

Main Methods:

• Synthesis of gold(I) coordination polymers ([Au(S-Ar^f)]_n).
• Characterization using DSC, SEM-EDX, TGA, IR, and PL spectroscopy.
• Transformation reactions with pyridine and DMSO.
• Structural elucidation of new complexes via single-crystal X-ray diffraction (SCXRD).
• Quantum-chemical calculations to study Au···Au interactions.

Main Results:

• Successful synthesis of [Au(S-Ar^f)]_n polymers from HS-Ar^f and Au(I).
• Transformation into [{Au(py)₂}{Au(S-Ar^f)₂}]_n complexes with linear cationic and anionic gold units linked by Au···Au interactions.
• Discovery of a unique polymeric structure [Au₄(S-C₆F₄-CF₃)₄]_n·nDMSO upon reaction with DMSO.
• Detailed structural analysis of the novel polymeric complexes.

Conclusions:

• Developed an atom-economy method for synthesizing gold(I) coordination polymers with fluorinated aryl thiolates.
• Demonstrated the ability to transform these polymers into new complex structures with tunable properties.
• Highlighted the significance of Au···Au interactions in stabilizing the extended chain structures.