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
C2 - 24171644
AN - SCOPUS:84890481222
SN - 0002-7863
VL - 135
SP - 18609
EP - 18620
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -