Relative unidirectional translation in an artificial molecular assembly fueled by light

Hao Li, Chuyang Cheng, Paul R. McGonigal, Albert C. Fahrenbach, Marco Frasconi, Wei Guang Liu, Zhixue Zhu, Yanli Zhao, Chenfeng Ke, Juying Lei, Ryan M. Young, Scott M. Dyar, Dick T. Co, Ying Wei Yang, Youssry Y. Botros, William A. Goddard, Michael R. Wasielewski, R. Dean Astumian, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticle

71 Scopus citations

Abstract

Motor molecules present in nature convert energy inputs, such as a chemical fuel or incident photons of light, into directed motion and force biochemical systems away from thermal equilibrium. The ability not only to control relative movements of components in molecules but also to drive their components preferentially in one direction relative to each other using versatile stimuli is one of the keys to future technological applications. Herein, we describe a wholly synthetic small-molecule system that, under the influence of chemical reagents, electrical potential, or visible light, undergoes unidirectional relative translational motion. Altering the redox state of a cyclobis(paraquat-p-phenylene) ring simultaneously (i) inverts the relative heights of kinetic barriers presented by the two termini - one a neutral 2-isopropylphenyl group and the other a positively charged 3,5- dimethylpyridinium unit - of a constitutionally asymmetric dumbbell, which can impair the threading/dethreading of a [2]pseudorotaxane, and (ii) controls the ring's affinity for a 1,5-dioxynaphthalene binding site located in the dumbbell's central core. The formation and subsequent dissociation of the [2]pseudorotaxane by passage of the ring over the neutral and positively charged termini of the dumbbell component in one, and only one, direction relatively defined has been demonstrated by (i) spectroscopic (1H NMR and UV/vis) means and cyclic voltammetry as well as with (ii) DFT calculations and by (iii) comparison with control compounds in the shape of constitutionally symmetrical [2]pseudorotaxanes, one with two positively charged ends and the other with two neutral ends. The operation of the system relies solely on reversible, yet stable, noncovalent bonding interactions. Moreover, in the presence of a photosensitizer, visible-light energy is the only fuel source that is needed to drive the unidirectional molecular translation, making it feasible to repeat the operation numerous times without the buildup of byproducts.

Original languageEnglish (US)
Pages (from-to)18609-18620
Number of pages12
JournalJournal of the American Chemical Society
Volume135
Issue number49
DOIs
StatePublished - Dec 11 2013

ASJC Scopus subject areas

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

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    Li, H., Cheng, C., McGonigal, P. R., Fahrenbach, A. C., Frasconi, M., Liu, W. G., Zhu, Z., Zhao, Y., Ke, C., Lei, J., Young, R. M., Dyar, S. M., Co, D. T., Yang, Y. W., Botros, Y. Y., Goddard, W. A., Wasielewski, M. R., Astumian, R. D., & Stoddart, J. F. (2013). Relative unidirectional translation in an artificial molecular assembly fueled by light. Journal of the American Chemical Society, 135(49), 18609-18620. https://doi.org/10.1021/ja4094204