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

doi:10.1021/ja4094204

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 journal › Article › peer-review

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 language	English
Pages (from-to)	18609-18620
Number of pages	12
Journal	Journal of the American Chemical Society
Volume	135
Issue number	49
DOIs	https://doi.org/10.1021/ja4094204
Publication status	Published - 11 Dec 2013

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10.1021/ja4094204

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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

@article{42e826ec91a24dea9bd00624672c5ecf,

title = "Relative unidirectional translation in an artificial molecular assembly fueled by light",

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.",

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

year = "2013",

month = dec,

day = "11",

doi = "10.1021/ja4094204",

language = "English",

volume = "135",

pages = "18609--18620",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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Li, H, Cheng, C, McGonigal, PR, Fahrenbach, AC, Frasconi, M, Liu, WG, Zhu, Z, Zhao, Y, Ke, C, Lei, J, Young, RM, Dyar, SM, Co, DT, Yang, YW, Botros, YY, Goddard, WA, Wasielewski, MR, Astumian, RD & Stoddart, JF 2013, 'Relative unidirectional translation in an artificial molecular assembly fueled by light', Journal of the American Chemical Society, vol. 135, no. 49, pp. 18609-18620. https://doi.org/10.1021/ja4094204

TY - JOUR

T1 - Relative unidirectional translation in an artificial molecular assembly fueled by light

AU - Li, Hao

AU - Cheng, Chuyang

AU - McGonigal, Paul R.

AU - Fahrenbach, Albert C.

AU - Frasconi, Marco

AU - Liu, Wei Guang

AU - Zhu, Zhixue

AU - Zhao, Yanli

AU - Ke, Chenfeng

AU - Lei, Juying

AU - Young, Ryan M.

AU - Dyar, Scott M.

AU - Co, Dick T.

AU - Yang, Ying Wei

AU - Botros, Youssry Y.

AU - Goddard, William A.

AU - Wasielewski, Michael R.

AU - Astumian, R. Dean

AU - Stoddart, J. Fraser

PY - 2013/12/11

Y1 - 2013/12/11

N2 - 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.

AB - 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.

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U2 - 10.1021/ja4094204

DO - 10.1021/ja4094204

M3 - Article

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EP - 18620

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 49

ER -

Relative unidirectional translation in an artificial molecular assembly fueled by light

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