Mechanically stabilized tetrathiafulvalene radical dimers

Coskun, A. et al. (2011) Mechanically stabilized tetrathiafulvalene radical dimers. Journal of the American Chemical Society, 133(12), pp. 4538-4547. (doi: 10.1021/ja110584c)

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Two donor-acceptor [3]catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4'-biphenylene), as the pi-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the pi-electron rich components have been investigated in order to study their ability to form TTF radical dimers. It has been proven that the mechanically interlocked nature of the [3]catenanes facilitates the formation of the TTF radical dimers under redox control, allowing an investigation to be performed on these intermolecular interactions in a so-called ``molecular flask'' under ambient conditions in considerable detail. In addition, it has also been shown that the stability of the TTF radical-cation dimers can be tuned by varying the secondary binding motifs in the [3]catenanes. By replacing the DNP station with a butadiyne group, the distribution of the TTF radical-cation dimer can be changed from 60% to 100%. These findings have been established by several techniques including cyclic voltammetry, spectroelectrochemistry and UV-vis-NIR and EPR spectroscopies, as well as with X-ray diffraction analysis which has provided a range of solid-state crystal structures. The experimental data are also supported by high-level DFT calculations. The results contribute significantly to our fundamental understanding of the interactions within the TTF radical dimers.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Forgan, Professor Ross
Authors: Coskun, A., Spruell, J.M., Barin, G., Fahrenbach, A.C., Forgan, R.S., Colvin, M.T., Carmieli, R., Benitez, D., Tkatchouk, E., Friedman, D.C., Sarjeant, A.A., Wasielewski, M.R., Goddard, W.A., and Stoddart, J.F.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
Published Online:02 March 2011

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