Engineering Supramolecular Hybrid Architectures with Directional Organofluorine Bonds

Understanding how chemical modifications alter the atomic-scale organization of materials is of fundamental importance in materials engineering and the target of considerable efforts in computational prediction. Incorporating covalent and noncovalent interactions in designing crystals while "piggybacking" on the driving force of molecular self-assembly has augmented efforts to understand the emergence of complex structures using directed synthesis. In this work, microcrystalline powders of the silver 2-, 3-, and 4-fluorobenzenethiolates are prepared and their structures are resolved by small-molecule serial femtosecond X-ray crystallography. These three compounds enable the emergence and role of supramolecular synthons in the crystal structures of 3D metal-organic chalcogenolates to be examined. The unique divergence in their optoelectronic, morphological, and structural behaviors is assessed. The extent of C-H-F interactions and their influence on the structure and the observed trends in the thermal stability of the crystals are quantified through theoretical calculations and thermogravimetric analysis. Exploiting noncovalent interactions in designing functional hybrid material systems is an attractive and efficient process for gaining atomic-level organization. Modifying the nature, steric factors, and electronegativity of functional groups used in building supramolecular architectures serves as a frontier to understanding material properties and how to arrange them into remarkable functional materials.image (c) 2023 WILEY-VCH GmbH