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Tetrathiafulvalene Crowns: Redox‐Switchable Ligands
Author(s) -
Le Derf Franck,
Mazari Miloud,
Mercier Nicolas,
Levillain Eric,
Trippé Gaëlle,
Riou Amédée,
Richomme Pascal,
Becher Jan,
Garín Javier,
Orduna Jesus,
GallegoPlanas Nuria,
Gorgues Alain,
Sallé Marc
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010119)7:2<447::aid-chem447>3.0.co;2-a
Subject(s) - tetrathiafulvalene , cyclic voltammetry , planarity testing , redox , chemistry , metal , crystallography , electrochemistry , inorganic chemistry , molecule , electrode , organic chemistry
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) π system and correctly oriented coordinating 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.