Template Effect of Tetrathiafulvalene in the Formation of Cyclobis(paraquat-p-phenylene)

Abstract

[reaction: see text] The template effect exerted by tetrathiafulvalene (TTF) in the ring-closure reaction of the trication 5(3+) yielding cyclobis(paraquat-p-phenylene) has been quantitatively evaluated in acetonitrile at 62 degrees C with UV-vis spectrophotometry. The rate of ring closure of the trication 5(3+) largely increases in the presence of the template (a maximum increase of ca. 80 times at [TTF] approximately 0.14 M). The results are compared with those of other aromatic templates, 2 and 3, that were provided with polyethereal sidearms and indicate that the template ability of tetrathiafulvalene is comparable or better than that of the others.

Quantifying the working stroke of tetrathiafulvalene-based electrochemically-driven linear motor-molecules

“…Finally, the 1 : 1 complex formation between CBPQT 4+ and structurally modified TTF derivatives has been investigated, 14 and it has been concluded 15 that the strength of the binding between TTF derivatives and CBPQT 4+ is strongly dependent on the p-electron donating ability of the TTF derivatives. " Beside CBPQT 4+ being able to host TTF and its derivatives, it has very recently been demonstrated 16 that TTF can be used as an efficient template for the synthesis of CBPQT 4+ . I Based on the half-wave potentials, there is a 16 mV driving force for this reaction.…”

Inclusion Complexes Containing Quaternary Azaaromatic Moieties

“…106 The conformational sensing mechanism of 49 and 50 for halide ion is shown below. 109,110 The above study indicates that the electron-rich molecule TTF, which does not possess polyethereal side chains has a higher template ability than that of such electron-rich aromatic molecules containing polyethereal side chains as 54 or 55. The results of UV-Vis spectroscopy have shown that the reaction affording 53 is ca 80 times faster in the presence of TTF.…”

Template-directed nonenzymatic oligonucleotide synthesis: lessons from synthetic chemistry

“…Later on, the Ercolani group [55][56][57][58][59][60][61] demonstrated in multiple instances over the course of a decade that the same principle holds true in the template-directed synthesis of the π-electron-poor tetracationic cyclobis(paraquat-p-phenylene) (CBPQT 4+ ) ring, first reported [62] by the Stoddart group, using a variety of π-electron-rich donors as templates. These donors bind more tightly to the transition state involving the final S N 2 reaction that leads to the cyclized product than they do to the acyclic substrate, and so accelerate the rate of reaction.…”