A redox-active reverse donor-acceptor bistable [2]rotaxane

Sanjeev K. Dey, Ali Coskun, Albert C. Fahrenbach, Gokhan Barin, Ashish N. Basuray, Ali Trabolsi, Youssry Y. Botros, J. Fraser Stoddart

    Research output: Contribution to journalArticle

    Abstract

    The synthesis and the dynamic behavior of a bistable [2]rotaxane, based on a reverse donor-acceptor motif containing naphthalene diimide (NpI) and 4,40-bipyridinium (BIPY2+) as two electron-deficient stations and bis-1,5-dioxynaphthalene[38]crown-10 (BDNP38C10) as the electron-rich ring, is described. A functionalized tetraarylmethane moiety has been incorporated between the two stations in order to control the free energy barrier for the shuttling of the BDNP38C10 on the dumbbell component. The bistable [2]rotaxane was synthesized using the so-called "threading-followed-bystoppering" approach and characterized by NMR spectroscopy and mass spectrometry. Initially, the BDNP38C10 ring resides on the NpI station on account of the synthetic approach employed in the synthesis of the bistable [2]rotaxane. 1H NMR spectroscopy was used to follow the equilibration process between the two translational isomers of the bistable [2]rotaxane-namely, NpI ⊂ BDNP38C10 and BIPY2+ ⊂BDNP38C10. After 72 h, equilibrium was reached with a 3: 2 ratio of the two translational isomers in favor of the NpI3BDNP38C10 co-conformation in CD3CN. The rate of relaxation of the crown ether from NpI ⊂ BDNP38C10 back to BIPY2+ ⊂ BDNP38C10 was associated with a rate constant of 2.2 ± 0.3 × 10-5 s-1 (t1/2 = 3.4 h), corresponding to a free energy of activation of 23.8 ± 0.1 kcal mol-1. Cyclic voltammetry (CV) reveals that the BDNP38C10 ring can be enticed to pass over the speed bump onto the neutral BIPY0 unit upon the generation of the NpI2- dianion, even although the neutral BIPY0 has presumably little or no affinity for the BDNP38C10 ring.

    Original languageEnglish (US)
    Pages (from-to)1046-1053
    Number of pages8
    JournalChemical Science
    Volume2
    Issue number6
    DOIs
    StatePublished - Jun 1 2011

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    Rotaxanes
    Isomers
    Nuclear magnetic resonance spectroscopy
    Free energy
    Crown Ethers
    Electrons
    Energy barriers
    Cyclic voltammetry
    Mass spectrometry
    Conformations
    Rate constants
    Chemical activation
    Oxidation-Reduction
    naphthalenediimide

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Dey, S. K., Coskun, A., Fahrenbach, A. C., Barin, G., Basuray, A. N., Trabolsi, A., ... Fraser Stoddart, J. (2011). A redox-active reverse donor-acceptor bistable [2]rotaxane. Chemical Science, 2(6), 1046-1053. https://doi.org/10.1039/c0sc00586j

    A redox-active reverse donor-acceptor bistable [2]rotaxane. / Dey, Sanjeev K.; Coskun, Ali; Fahrenbach, Albert C.; Barin, Gokhan; Basuray, Ashish N.; Trabolsi, Ali; Botros, Youssry Y.; Fraser Stoddart, J.

    In: Chemical Science, Vol. 2, No. 6, 01.06.2011, p. 1046-1053.

    Research output: Contribution to journalArticle

    Dey, SK, Coskun, A, Fahrenbach, AC, Barin, G, Basuray, AN, Trabolsi, A, Botros, YY & Fraser Stoddart, J 2011, 'A redox-active reverse donor-acceptor bistable [2]rotaxane', Chemical Science, vol. 2, no. 6, pp. 1046-1053. https://doi.org/10.1039/c0sc00586j
    Dey SK, Coskun A, Fahrenbach AC, Barin G, Basuray AN, Trabolsi A et al. A redox-active reverse donor-acceptor bistable [2]rotaxane. Chemical Science. 2011 Jun 1;2(6):1046-1053. https://doi.org/10.1039/c0sc00586j
    Dey, Sanjeev K. ; Coskun, Ali ; Fahrenbach, Albert C. ; Barin, Gokhan ; Basuray, Ashish N. ; Trabolsi, Ali ; Botros, Youssry Y. ; Fraser Stoddart, J. / A redox-active reverse donor-acceptor bistable [2]rotaxane. In: Chemical Science. 2011 ; Vol. 2, No. 6. pp. 1046-1053.
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