Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane

Cheng Wang, Scott M. Dyar, Dennis Cao, Albert C. Fahrenbach, Noah Horwitz, Michael T. Colvin, Raanan Carmieli, Charlotte L. Stern, Sanjeev K. Dey, Michael R Wasielewski, J. Fraser Stoddart

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4′-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4′-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO and STTFS. The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT 4+ ring. After a one-electron oxidation, a 70:30 ratio of OTTFO to STTFS is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT 4+ ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units.

Original languageEnglish
Pages (from-to)19136-19145
Number of pages10
JournalJournal of the American Chemical Society
Volume134
Issue number46
DOIs
Publication statusPublished - Nov 21 2012

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Dimerization
Polyethers
Oxidation-Reduction
Cations
Positive ions
Electrons
Dimers
Electron Spin Resonance Spectroscopy
Paramagnetic resonance
Spectroscopy
Spectrum Analysis
Oxidation
Electrochemical Techniques
Paraquat
Titration
Isomers
Electronic properties
Constitution and Bylaws
tetrathiafulvalene
catenane

ASJC Scopus subject areas

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

Cite this

Wang, C., Dyar, S. M., Cao, D., Fahrenbach, A. C., Horwitz, N., Colvin, M. T., ... Stoddart, J. F. (2012). Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane. Journal of the American Chemical Society, 134(46), 19136-19145. https://doi.org/10.1021/ja307577t

Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane. / Wang, Cheng; Dyar, Scott M.; Cao, Dennis; Fahrenbach, Albert C.; Horwitz, Noah; Colvin, Michael T.; Carmieli, Raanan; Stern, Charlotte L.; Dey, Sanjeev K.; Wasielewski, Michael R; Stoddart, J. Fraser.

In: Journal of the American Chemical Society, Vol. 134, No. 46, 21.11.2012, p. 19136-19145.

Research output: Contribution to journalArticle

Wang, C, Dyar, SM, Cao, D, Fahrenbach, AC, Horwitz, N, Colvin, MT, Carmieli, R, Stern, CL, Dey, SK, Wasielewski, MR & Stoddart, JF 2012, 'Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane', Journal of the American Chemical Society, vol. 134, no. 46, pp. 19136-19145. https://doi.org/10.1021/ja307577t
Wang C, Dyar SM, Cao D, Fahrenbach AC, Horwitz N, Colvin MT et al. Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane. Journal of the American Chemical Society. 2012 Nov 21;134(46):19136-19145. https://doi.org/10.1021/ja307577t
Wang, Cheng ; Dyar, Scott M. ; Cao, Dennis ; Fahrenbach, Albert C. ; Horwitz, Noah ; Colvin, Michael T. ; Carmieli, Raanan ; Stern, Charlotte L. ; Dey, Sanjeev K. ; Wasielewski, Michael R ; Stoddart, J. Fraser. / Tetrathiafulvalene hetero radical cation dimerization in a redox-active [2]catenane. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 46. pp. 19136-19145.
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abstract = "The electronic properties of tetrathiafulvalene (TTF) can be tuned by attaching electron-donating or electron-withdrawing substituents. An electron-rich macrocyclic polyether containing two TTF units of different constitutions, namely 4,4′-bis(hydroxymethyl)tetrathiafulvalene (OTTFO) and 4,4′-bisthiotetrathiafulvalene (STTFS), has been synthesized. On two-electron oxidation, a hetero radical dimer is formed between OTTFO • and STTFS•. The redox behavior of the macrocyclic polyether has been investigated by electrochemical techniques and UV-vis and electron paramagnetic resonance (EPR) spectroscopies. The [2]catenane in which the macrocyclic polyether is mechanically interlocked with the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring has also been prepared using template-directed protocols. In the case of the [2]catenane, the formation of the TTF hetero radical dimer is prevented sterically by the CBPQT 4+ ring. After a one-electron oxidation, a 70:30 ratio of OTTFO • to STTFS• is present at equilibrium, and, as a result, two translational isomers of the [2]catenane associated with these electronically different isomeric states transpire. EPR titration spectroscopy and simulations reveal that the radical states of the two constitutionally different TTF units in the [2]catenane still experience long-range electronic intramolecular coupling interactions, despite the presence of the CBPQT 4+ ring, when one or both of them are oxidized to the radical cationic state. These findings in the case of both the free macrocyclic polyether and the [2]catenane have led to a deeper fundamental understanding of the mechanism of radical cation dimer formation between constitutionally different TTF units.",
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