Engineering Supramolecular Hybrid Architectures with Directional Organofluorine Bonds

Area of Science:

• Materials Science
• Crystallography
• Supramolecular Chemistry

Background:

• Understanding chemical modifications' impact on atomic-scale material organization is crucial for materials engineering.
• Molecular self-assembly and directed synthesis are key strategies for creating complex crystal structures.
• Metal-organic chalcogenolates (MOChas) offer a platform to study supramolecular interactions.

Purpose of the Study:

• To investigate the role of supramolecular synthons in the crystal structures of silver 2-, 3-, and 4-fluorobenzenethiolates.
• To analyze the influence of C-H···F interactions on the structural and thermal properties of these compounds.
• To correlate structural findings with optoelectronic and morphological behavior.

Main Methods:

• Preparation of microcrystalline powders of silver 2-, 3-, and 4-fluorobenzenethiolates.
• Structure determination using small molecule serial femtosecond X-ray crystallography (smSFX).
• Quantification of C-H···F interactions and thermal stability via theoretical calculations and thermogravimetric analysis.

Main Results:

• The crystal structures of three silver fluorobenzenethiolates were resolved, revealing distinct supramolecular arrangements.
• The extent of C-H···F interactions was quantified and shown to influence crystal packing.
• Trends in thermal stability were observed and correlated with structural features and C-H···F interactions.

Conclusions:

• Supramolecular synthons play a significant role in directing the assembly of metal-organic chalcogenolates.
• C-H···F interactions are critical in governing the structure and thermal stability of these materials.
• The study provides fundamental insights into structure-property relationships in functional organic materials.