Trinuclear Copper(I) and Silver(I) Complexes of a Pentafluorosulfanyl-Decorated Pyrazolate

Area of Science:

• Organometallic Chemistry
• Fluorine Chemistry
• Materials Science

Background:

• Coinage metal pyrazolates are important coordination compounds.
• Fluorinated organic groups significantly influence molecular properties.
• The SF5 group offers unique electronic and steric effects compared to CF3.

Purpose of the Study:

• Synthesize and characterize novel fluorinated coinage metal pyrazolates featuring the SF5 group.
• Compare the properties of SF5-containing complexes with their CF3 analogs.
• Investigate the impact of SF5 substituents on π-acidity, arene binding, and photoluminescence.

Main Methods:

• Synthesis of {[3-(SF5)Pz]M}3 (M = Cu, Ag) complexes.
• X-ray crystallography for structural determination.
• Photophysical measurements (phosphorescence and fluorescence).
• Computational studies (DFT) for electronic structure and interactions.

Main Results:

• First synthesis of SF5-functionalized coinage metal pyrazolates reported.
• X-ray analysis revealed distinct ligand orientations, metallophilic interactions, and supramolecular assemblies.
• SF5 complexes formed sandwich adducts with benzene, showing enhanced π-acidity and arene binding versus CF3 analogs.
• Copper complexes displayed long-lived phosphorescence; silver complexes showed fast fluorescence, tunable by environment and interactions.

Conclusions:

• SF5-decorated pyrazolates exhibit enhanced π-acidity and arene-binding capabilities.
• These compounds are promising candidates for molecular sensing and tunable luminescence.
• The study provides fundamental insights into structure-property relationships in fluorinated organometallic compounds.