Tetrathiafulvalene-calix[4]pyrrole: a versatile synthetic receptor for electron-deficient planar and spherical guests

The first tetrakis-tetrathiafulvalene-calix[4]pyrrole (TTF-C[4]P) was reported in 2004. Early on it and related π-extended TTF-C[4]Ps were found to function as both anion receptors and as hosts for planar electron deficient neutral guests, including nitroaromatic explosives. Anion binding was found...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2019-03, Vol.17 (1), p.2594-2613
Main Authors: Bähring, Steffen, Root, Harrison D, Sessler, Jonathan L, Jeppesen, Jan O
Format: Article
Language:English
Subjects:
Anions
Binding
Buckminsterfullerene
Cations
Conformation
Electron transfer
Electrons
Fullerenes
Organic chemistry
Receptor mechanisms
Receptors
Selectivity
Stoichiometry
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Summary:The first tetrakis-tetrathiafulvalene-calix[4]pyrrole (TTF-C[4]P) was reported in 2004. Early on it and related π-extended TTF-C[4]Ps were found to function as both anion receptors and as hosts for planar electron deficient neutral guests, including nitroaromatic explosives. Anion binding was found to occur with a 1 : 1 binding stoichiometry and to stabilise the cone C[4]P conformation, whereas planar electron deficient guests were bound in a cooperative 1 : 2 fashion to the 1,3-alternate conformer. Addition of strongly complexing anions was found to trigger release of the electron deficient guests concurrent with a conformational change to the cone form. Subsequent studies led to the discovery of anion-induced complexation with C 60 , and the finding that the resulting complexes would support fast photoinduced electron transfer events. Synthetic advances then led to the preparation of nonsymmetric TTF-C[4]Ps where a single moiety organises the receptor in either the 1,3-alternate conformation or the partial cone conformation, thus modifying both selectivity and sensitivity. TTF-C[4]P-based stimulus responsive systems, that rely on anions and cations as controlling inputs, have also been developed and studied in recent years. This review provides a summary of TTF-C[4]P-related chemistry. The chemistry of tetrathiafulvalene-calix[4]pyrrole is reviewed with focus on conformational behavior, receptor properties and ionically controlled electron transfer processes.
ISSN:1477-0520
1477-0539
DOI:10.1039/c8ob02514b