Tetrathiafulvalene Crowns: Redox-Switchable Ligands

✍ Scribed by Franck Le Derf; Miloud Mazari; Nicolas Mercier; Eric Levillain; Gaëlle Trippé; Amédée Riou; Pascal Richomme; Jan Becher; Javier Garín; Jesus Orduna; Nuria Gallego-Planas; Alain Gorgues; Marc Sallé

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 335 KB
• Volume: 7
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/1521-3765(20010119)7:2<447::aid-chem447>3.0.co;2-a

✦ Synopsis

A series of redox-responsive ligands that associate the electroactive tetrathiafulvalene core with polyether subunits of various lengths has been synthesized. X-ray structures are provided for each of the free ligands. The requisite structural criteria for reaching switchable ligands are satisfied for the largest macrocycles, that is, planarity of the 1,1',3,3'-tetrathiafulvalene (TTF) p system and correctly oriented coordi-nating atoms. The ability of these ligands to recognize various metal cations as a function of the cavity size has been investigated by various techniques (LSIMS, 1 H NMR, and UV/Vis spectroscopy, cyclic voltammetry). These systems exhibit an unprecedented high coordination ability among TTF crown ethers. Their switchable ligating properties have been confirmed by cyclic voltammetry, and metal-cation complexation has been illustrated by X-ray structures of three of the corresponding metal complexes (Pb 2 , Sr 2 , and Ba 2 ). Solid-state structures of these complexes display original packing modes with channel-like arrangements.