Molecular-mechanical switching at the nanoparticle-solvent interface

Practice and theory

Ali Coskun, Paul J. Wesson, Rafal Klajn, Ali Trabolsi, Lei Fang, Mark A. Olson, Sanjeev K. Dey, Bartosz A. Grzybowski, J. Fraser Stoddart

    Research output: Contribution to journalArticle

    Abstract

    A range (Au, Pt, Pd) of metal nanoparticles (MNPs) has been prepared and functionalized with (a) redox-active stalks containing tetrathiafulvalene (TTF) units, (b) [2]pseudorotaxanes formed between these stalks and cyclobis(paraquat-p-phenylene) (CBPQT4+) rings, and (c) bistable [2]rotaxane molecules where the dumbbell component contains a 1,5-dioxynaphthalene (DNP) unit, as well as a TTF unit, encircled by a CBPQT4+ ring. It transpires that the molecules present in (a) and (c) and the supermolecules described in (b) retain their switching characteristics, previously observed in solution, when they are immobilized onto MNPs. Moreover, their oxidation potentials depend on the fraction, χ, of the molecules or supermolecules on the surface of the nanoparticles. A variation in χ affects the oxidation potentials of the TTF units to the extent that switching can be subjected to fine tuning as a result. Specifically, increasing χ results in positive shifts (i) in the oxidation potentials of the TTF unit in (a)-(c) and (ii) the reduction potentials of the CBPQT4+ rings in (c). These shifts can be attributed to an increase in the electrostatic potential surrounding the MNPs. Both the magnitude and the direction of these shifts are reproduced by a model, based on the Poisson-Boltzmann equation coupled with charge-regulating boundary conditions. Furthermore, the kinetics of relaxation from the metastable state coconformation (MSCC) to the groundstate coconformation (GSCC) of the bistable [2]rotaxane molecules also depends on χ, as well as on the nanoparticle diameter. Increasing either of these parameters accelerates the rate of relaxation from the MSCC to the GSCC. This rate is a function of (i) the activation energy for the relaxation process associated with the bistable [2]rotaxane molecules in solution and (ii) the electrostatic potential surrounding the MNPs. The electrostatic potential depends on (i) the diameter of the MNPs, (ii) the amount of the bistable [2]rotaxane molecules on the surface of the MNPs, and (iii) the equilibrium distribution of the CBPQT4+ rings between the DNP and TTF recognition sites in the GSCC. This electrostatic potential has also been quantified using the Poisson-Boltzmann equation, leading to faithful estimates of the rate constants.

    Original languageEnglish (US)
    Pages (from-to)4310-4320
    Number of pages11
    JournalJournal of the American Chemical Society
    Volume132
    Issue number12
    DOIs
    StatePublished - Mar 31 2010

    Fingerprint

    Metal Nanoparticles
    Rotaxanes
    Metal nanoparticles
    Nanoparticles
    Static Electricity
    Molecules
    Electrostatics
    Boltzmann equation
    Oxidation
    Paraquat
    Relaxation processes
    Oxidation-Reduction
    Rate constants
    Tuning
    Activation energy
    tetrathiafulvalene
    Boundary conditions
    Kinetics

    ASJC Scopus subject areas

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

    Cite this

    Coskun, A., Wesson, P. J., Klajn, R., Trabolsi, A., Fang, L., Olson, M. A., ... Fraser Stoddart, J. (2010). Molecular-mechanical switching at the nanoparticle-solvent interface: Practice and theory. Journal of the American Chemical Society, 132(12), 4310-4320. https://doi.org/10.1021/ja9102327

    Molecular-mechanical switching at the nanoparticle-solvent interface : Practice and theory. / Coskun, Ali; Wesson, Paul J.; Klajn, Rafal; Trabolsi, Ali; Fang, Lei; Olson, Mark A.; Dey, Sanjeev K.; Grzybowski, Bartosz A.; Fraser Stoddart, J.

    In: Journal of the American Chemical Society, Vol. 132, No. 12, 31.03.2010, p. 4310-4320.

    Research output: Contribution to journalArticle

    Coskun, A, Wesson, PJ, Klajn, R, Trabolsi, A, Fang, L, Olson, MA, Dey, SK, Grzybowski, BA & Fraser Stoddart, J 2010, 'Molecular-mechanical switching at the nanoparticle-solvent interface: Practice and theory', Journal of the American Chemical Society, vol. 132, no. 12, pp. 4310-4320. https://doi.org/10.1021/ja9102327
    Coskun, Ali ; Wesson, Paul J. ; Klajn, Rafal ; Trabolsi, Ali ; Fang, Lei ; Olson, Mark A. ; Dey, Sanjeev K. ; Grzybowski, Bartosz A. ; Fraser Stoddart, J. / Molecular-mechanical switching at the nanoparticle-solvent interface : Practice and theory. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 12. pp. 4310-4320.
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    AU - Trabolsi, Ali

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    AU - Olson, Mark A.

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