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Balzani V, Credi A, Mattersteig G, et al. Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs. J Org Chem. 2000;65(7):1924-36doi: 10.1021/jo991781t.
Balzani, V., Credi, A., Mattersteig, G., Matthews, O. A., Raymo, F. M., Stoddart, J. F., Venturi, M., White, A. J., & Williams, D. J. (2000). Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs. The Journal of organic chemistry, 65(7), 1924-36. https://doi.org/10.1021/jo991781t
Balzani, et al. "Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs." The Journal of organic chemistry vol. 65,7 (2000): 1924-36. doi: https://doi.org/10.1021/jo991781t
Balzani V, Credi A, Mattersteig G, Matthews OA, Raymo FM, Stoddart JF, Venturi M, White AJ, Williams DJ. Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs. J Org Chem. 2000 Apr 07;65(7):1924-36. doi: 10.1021/jo991781t. PMID: 10774011.
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J Org Chem. 2000 Apr 07;65(7):1924-36. doi: 10.1021/jo991781t.

Switching of pseudorotaxanes and catenanes incorporating a tetrathiafulvalene unit by redox and chemical inputs.

The Journal of organic chemistry

Balzani, Credi, Mattersteig, Matthews, Raymo, Stoddart, Venturi, White, Williams

Affiliations

  1. Dipartimento di Chimica G. Ciamician, Universita di Bologna, Italy.

PMID: 10774011 DOI: 10.1021/jo991781t

Abstract

An acyclic polyether 1a, incorporating a central tetrathiafulvalene (TTF) electron donor unit and two 4-tert-butylphenoxy groups at its termini, has been synthesized. Two macrocyclic polyethers containing two different electron donors, namely a TTF unit with, in one case, a 1,4-dioxybenzene ring (2a), and, in the other case (2b), a 1,5-dioxynaphthalene ring system, have also been synthesized. These two macrocyclic polyethers have been mechanically interlocked in kinetically controlled template-directed syntheses with cyclobis(paraquat-p-phenylene) cyclophane (3(4+)) to afford the [2]catenanes 2a/3(4+) and 2b/3(4+), respectively. X-ray crystallography reveals that the [2]-catenane 2b/3(4+) has the TTF unit of 2b located inside the cavity of 3(4+). The spectroscopic (UV/vis and 1H NMR) and electrochemical properties of compounds 1a, 2a, 2b, 2a/3(4+), and 2b/3(4+) and of the [2]pseudorotaxane 1a.3(4+) were investigated. The absorption and emission properties of the mono- and dioxidized forms of the TTF unit in these various species have also been studied. The results obtained in acetonitrile solution can be summarized as follows. (a) While TTF2+ exhibits a strong fluorescence, no emission can be observed for the TTF2+ units contained in the polyethers and in their pseudorotaxanes and catenanes. (b) A donor-acceptor absorption band is observed upon two-electron oxidation of the TTF unit in the macrocyclic polyethers 2a and 2b. (c) The spontaneous self-assembly of 1a and 3(4+) to give the [2]pseudorotaxane 1a.3(4+) is strongly favored (Kass. = 5 x 10(5) L mol-1) but slow (at 296 K, k = 11.3 L mol-1 s-1 and delta G++ = 15.9 kcal mol-1) because of the steric hindrance associated with the bulky end groups of 1a. (d) In the pseudorotaxane 1a.3(4+), the reversible displacement of the cyclophane from the TTF unit in the threadlike substrate occurs on oxidation/reduction of its electroactive components. (e) Switching between the two translational isomers of the catenanes 2a/3(4+) and 2b/3(4+) occurs by cyclic oxidation and reduction of the TTF unit contained in 2a and in 2b, respectively. (f) Addition of o-chloroanil to the pseudorotaxane 1a.3(4+) and to the catenanes 2a/3(4+) and 2b/3(4+) causes the displacement of the TTF unit from the cavity of the cyclophane 3(4+) because of the formation of an adduct between the TTF unit and o-chloroanil.

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