A multistate switchable [3]rotacatenane

Gokhan Barin, Ali Coskun, Douglas C. Friedman, Mark A. Olson, Michael T. Colvin, Raanan Carmielli, Sanjeev K. Dey, O. Altan Bozdemir, Michael R Wasielewski, J. Fraser Stoddart

Research output: Contribution to journalArticle

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Abstract

Rotacatenanes are exotic molecular compounds that can be visualized as a unique combination of a [2]catenane and a [2]rotaxane, thereby combining both the circumrotation of the ring component (rotary motion) and the shuttling of the dumbbell component (translational motion) in one structure. Herein, we describe a strategy for the synthesis of a new switchable [3]rotacatenane and the investigation of its switching properties, which rely on the formation of tetrathiafulvalene (TTF) radical π-dimer interactions-namely, the mixed-valence state (TTF2)+. and the radical-cation dimer state (TTF+.)2-under ambient conditions. A template-directed approach, based on donor-acceptor interactions, has been developed, resulting in an improved yield of the key precursor [2]catenane, prior to rotacatenation. The nature of the binding between the [2]catenane and selected π-electron-rich templates has been elucidated by using X-ray crystallography and UV/Vis spectroscopy as well as isothermal titration microcalorimetry. The multistate switching mechanism of the [3]rotacatenane has been demonstrated by cyclic voltammetry and EPR spectroscopy. Most notably, the radical-cation dimer state (TTF+.)2 has been shown to enter into an equilibrium by forming the co-conformation in which the two 1,5-dioxynaphthalene (DNP) units co-occupy the cavity of tetracationic cyclophane, thus enforcing the separation of TTF radical-cation dimer (TTF +.)2. The population ratio of this equilibrium state was found to be 1:1. We believe that this research demonstrates the power of constructing complex molecular machines using template-directed protocols, enabling us to make the transition from simple molecular switches to their multistate variants for enhancing information storage in molecular electronic devices.

Original languageEnglish
Pages (from-to)213-222
Number of pages10
JournalChemistry - A European Journal
Volume17
Issue number1
DOIs
Publication statusPublished - Jan 3 2011

Fingerprint

Dimers
Positive ions
Cations
Molecular electronics
Rotaxanes
X ray crystallography
Ultraviolet spectroscopy
Titration
Cyclic voltammetry
Paramagnetic resonance
Conformations
Switches
Spectroscopy
Data storage equipment
tetrathiafulvalene
Electrons
catenane

Keywords

  • molecular switches
  • radical dimerization
  • rotacatenanes
  • template-directed synthesis
  • tetrathiafulvalenes

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Barin, G., Coskun, A., Friedman, D. C., Olson, M. A., Colvin, M. T., Carmielli, R., ... Stoddart, J. F. (2011). A multistate switchable [3]rotacatenane. Chemistry - A European Journal, 17(1), 213-222. https://doi.org/10.1002/chem.201002152

A multistate switchable [3]rotacatenane. / Barin, Gokhan; Coskun, Ali; Friedman, Douglas C.; Olson, Mark A.; Colvin, Michael T.; Carmielli, Raanan; Dey, Sanjeev K.; Bozdemir, O. Altan; Wasielewski, Michael R; Stoddart, J. Fraser.

In: Chemistry - A European Journal, Vol. 17, No. 1, 03.01.2011, p. 213-222.

Research output: Contribution to journalArticle

Barin, G, Coskun, A, Friedman, DC, Olson, MA, Colvin, MT, Carmielli, R, Dey, SK, Bozdemir, OA, Wasielewski, MR & Stoddart, JF 2011, 'A multistate switchable [3]rotacatenane', Chemistry - A European Journal, vol. 17, no. 1, pp. 213-222. https://doi.org/10.1002/chem.201002152
Barin G, Coskun A, Friedman DC, Olson MA, Colvin MT, Carmielli R et al. A multistate switchable [3]rotacatenane. Chemistry - A European Journal. 2011 Jan 3;17(1):213-222. https://doi.org/10.1002/chem.201002152
Barin, Gokhan ; Coskun, Ali ; Friedman, Douglas C. ; Olson, Mark A. ; Colvin, Michael T. ; Carmielli, Raanan ; Dey, Sanjeev K. ; Bozdemir, O. Altan ; Wasielewski, Michael R ; Stoddart, J. Fraser. / A multistate switchable [3]rotacatenane. In: Chemistry - A European Journal. 2011 ; Vol. 17, No. 1. pp. 213-222.
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