Tetrathiafulvalene Cyclophanes and Cage Molecules

Persistent Mixed‐Valence [(TTF)2]+. Dyad of a Chiral Bis(binaphthol)–tetrathiafulvalene (TTF) Derivative

“…Such splitting of the first oxidation wave is usually characteristic of the favoured formation of an intermediate mixedvalence TTF dyad (TTF) 2 + C, a species only rarely observed in a few TTF dimers and cyclophanes in which the two TTF are either covalently linked, [3,4] or when constrained within cagelike rigid structures. [5,6] A glycoluril-based TTF covalent dyad that associates into clip dimers under oxidative control provides another recent rare example.…”

“…A notable exception involves the case of arenes (naphthalene, fluoranthene, and so on) at high concentration and low temperature. [2] The only rare examples in which such a mixed-valence [(TTF) 2 ] + C species has been observed in solution are restricted to situations in which the two TTF moieties are forced to interact, either when covalently linked into TTF dimers [3] or cyclophanes, [4] or embedded within a cage, as an organic cucurbit [8]uril receptor [5] or a self-assembled coordination cage. [6] Besides these two situations, a stable self-association of TTF moieties within a [(TTF) 2 ] + C mixed-valence species has not been observed yet, but can be anticipated if specific non-covalent intermolecular interactions can simultaneously stabilise the dyadic association and hinder its precipitation.…”

Supramolecular Receptor Design: Anion‐Triggered Binding of C60

“…To date, a number of "molecular containers", including cyclodextrins, [26] (benzotri(benzonorbornadienes), [27] calixarenes, [28][29][30][31] calixnaphthalenes, [32] and cyclotriveratrylene, [33] have been used to achieve fullerene recognition. Porphyrins and metalloporphyrins, [34,35] which benefit from favorable van der Waals interactions with the p surface of fullerenes, have also been used to achieve C 60 recognition, as have individual tetrathiafulvalene [36,37] (TTF) subunits in the solid state. [38] However, in all cases the receptor is a discrete entity (that is, the product of fermentation or synthesis), rather than a scaffold built up through selfassembly.…”

Synthesis, crystal structure and biological activity of novel diester cyclophanes

“…Since then, cyclophanes have attracted a great deal of attention from organic scientists, various kinds of compounds have been synthesized and their structures and properties have been studied. [2][3][4][5][6] Cyclophanes play an important role in host-guest chemistry because they can recognize specific molecules or ions by forming various inclusion complexes. [7][8][9] In some reaction systems, the host-guest complex can simulate the high efficiency of enzyme catalysis, which means the reaction yield can be greatly improved.…”