Mechanically stabilized tetrathiafulvalene radical dimers

Ali Coskun, Jason M. Spruell, Gokhan Barin, Albert C. Fahrenbach, Ross S. Forgan, Michael T. Colvin, Raanan Carmieli, Diego Benítez, Ekaterina Tkatchouk, Douglas C. Friedman, Amy A. Sarjeant, Michael R. Wasielewski, William A. Goddard, J. Fraser Stoddart

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Abstract

Two donor-acceptor [3]catenanes-composed of a tetracationic molecular square, cyclobis(paraquat-4,4′-biphenylene), as the π-electron deficient ring and either two tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) containing macrocycles or two TTF-butadiyne-containing macrocycles as the π-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.

Original languageEnglish
Pages (from-to)4538-4547
Number of pages10
JournalJournal of the American Chemical Society
Volume133
Issue number12
DOIs
Publication statusPublished - Mar 30 2011

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Coskun, A., Spruell, J. M., Barin, G., Fahrenbach, A. C., Forgan, R. S., Colvin, M. T., Carmieli, R., Benítez, D., Tkatchouk, E., Friedman, D. C., Sarjeant, A. A., Wasielewski, M. R., Goddard, W. A., & Stoddart, J. F. (2011). Mechanically stabilized tetrathiafulvalene radical dimers. Journal of the American Chemical Society, 133(12), 4538-4547. https://doi.org/10.1021/ja110584c