Periphery Modification of Tetrathiafulvalenes: Recent Development and Applications.

Tetrathiafulvalene (TTF) and its analogs are fascinating molecules in materials science based on their excellent electron-donating abilities. This personal account describes recent advances in the synthesis of TTF analogs for functional materials via the palladium-catalyzed modification of peripheries of TTF analogs. We first consider three types of molecules: fluorophore-TTF hybrid molecules, multi-redox systems, and an organic ligand for metal-organic frameworks. These molecules were successfully synthesized via Stille coupling or palladium-catalyzed direct C-H arylation and their structural, electrochemical, and optical properties were clarified. Subsequently, phosphorus-substituted TTF analogs were successfully synthesized for future applications of redox-active phosphine ligands for metal catalysts. The development of these molecules can significantly affect the advancement of chemical science.