A Reversible, Unidirectional Molecular Rotary Motor Driven by Chemical Energy

Fletcher, Stephen P.; Dumur, Frédéric; Pollard, Michael M.; Feringa, Ben L.

doi:10.1126/science.1117090

Cited by 431 publications

(229 citation statements)

References 31 publications

Supporting

Mentioning

226

Contrasting

Unclassified

Order By: Relevance

“…22 Their designs culminated in a system that employed chemical reactions to bias a 120 degree rotation of a triptycene residue in one direction, 23 but attempts to extend this approach to repetitive 360 degree directional rotation proved unsuccessful. 24 Light-driven rotary molecular motors based on overcrowded alkenes 12,13 and imines 14,16 have been developed by the groups of Feringa and Lehn, while our group 25,26 and others [27][28][29] have made molecules in which the components can be rotated directionally step-wise by repetitively carrying out several chemical reactions in sequence. The latter systems all operate through Brownian ratchet mechanisms, differentiating the rates of random thermal motion of the components in each direction by the manipulation of kinetic (mainly steric) barriers.…”

mentioning

confidence: 99%

An autonomous chemically fuelled small-molecule motor

Wilson

Solà

Carlone

et al. 2016

Nature

442

438

View full text Add to dashboard Cite

We find that a bulky pyridine-based catalyst promotes carbonate-forming reactions that ratchet the displacement of the macrocycle away from the reactive sites on the track. Under reaction conditions where both attachment and cleavage of the Fmoc groups occur through different processes, and the cleavage reaction occurs at a rate independent of macrocycle location, net directional rotation of the molecular motor continues for as long as unreacted fuel remains. We anticipate that autonomous chemically-fuelled molecular motors will find application as engines for molecular nanotechnology. 2, 19,20

show abstract

mentioning

confidence: 99%

An autonomous chemically fuelled small-molecule motor

Wilson

Solà

Carlone

et al. 2016

Nature

442

438

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10] Whilst it is tempting to regard such multicomponent assemblies as "molecular meccano," 11 many aspects of classical mechanics become meaningless at this level of miniaturization. 12 For example, in the macroscopic world the equations of motion are governed by inertial terms (dependent on mass), but under the conditions that molecular machines operate viscous forces (governed by particle dimensions) and Brownian motion dominate mechanical behavior.…”

Section: Introductionmentioning

confidence: 99%

Bimodal dynamics of mechanically constrained hydrogen bonds revealed by vibrational photon echoes

Bodis

Yeremenko

Berná

et al. 2011

The Journal of Chemical Physics

View full text Add to dashboard Cite

Bimodal dynamics of mechanically constrained hydrogen bonds revealed by vibrational photon echoes Bodis, P.; Yeremenko, S.; Berna, J.; Buma, W.J.; Leigh, D.A.; Woutersen, S. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We have investigated the dynamics of the hydrogen bonds that connect the components of a [2]rotaxane in solution. In this rotaxane, the amide groups in the benzylic-amide macrocycle and the succinamide thread are connected by four equivalent N−H· · ·O=C hydrogen bonds. The fluctuations of these hydrogen bonds are mirrored by the frequency fluctuations of the NH-stretch modes, which are probed by means of three-pulse photon-echo peak shift spectroscopy. The hydrogen-bond fluctuations occur on three different time scales, with time constants of 0.1, 0.6, and ≥200 ps. Comparing these three time scales to the ones found in liquid formamide, which contains the same hydrogenbonded amide motif but without mechanical constraints, we find that the faster two components, which are associated with small-amplitude fluctuations in the strength of the N−H· · ·O=C hydrogen bonds, are very similar in the liquid and the rotaxane. However, the third component, which is associated with the breaking and subsequent reformation of hydrogen bonds, is found to be much slower in the rotaxane than in the liquid. It can be concluded that the mechanical bonding in a rotaxane does not influence the amplitude and time scale of the small-amplitude fluctuations of the hydrogen bonds, but strongly slows down the complete dissociation of these hydrogen bonds. This is probably because in a rotaxane breaking of the macrocycle-axle contacts is severely hindered by the mechanical constraints. The hydrogen-bond dynamics in rotaxane-based molecular machines can therefore be regarded as liquidlike on a time scale 1 ps and less, but structurally frozen on longer (up to at least 200 ps) time scales.

show abstract

“…36,[38][39][40][41] Stimuli such as thermal variations, electric fields, and photoinduction have been used as triggers for the conversion of chemical energy into mechanical work. 37,[42][43][44] Assemblies that convert chemical energy into directional motion can be achieved through isomerization reactions which are induced either from light or applied electric fields. 35,45,46 In these responsive materials, controlling the rate and pathway at which reactants transform to products is fundamental to harness mechanical actions for applicative purposes.…”

Section: Introductionmentioning

confidence: 99%

Chemical reactions induced by oscillating external fields in weak thermal environments

Craven

Bartsch

Hernandez

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

Chemical reaction rates must increasingly be determined in systems that evolve under the control of external stimuli. In these systems, when a reactant population is induced to cross an energy barrier through forcing from a temporally varying external field, the transition state that the reaction must pass through during the transformation from reactant to product is no longer a fixed geometric structure, but is instead timedependent. For a periodically forced model reaction, we develop a recrossing-free dividing surface that is attached to a transition state trajectory [T. Bartsch, R. Hernandez, and T. Uzer, Phys. Rev. Lett. 95, 058301 (2005)]. We have previously shown that for single-mode sinusoidal driving, the stability of the timevarying transition state directly determines the reaction rate [G. T. Craven, T. Bartsch, and R. Hernandez, J. Chem. Phys. 141, 041106 (2014)]. Here, we extend our previous work to the case of multi-mode driving waveforms. Excellent agreement is observed between the rates predicted by stability analysis and rates obtained through numerical calculation of the reactive flux. We also show that the optimal dividing surface and the resulting reaction rate for a reactive system driven by weak thermal noise can be approximated well using the transition state geometry of the underlying deterministic system. This agreement persists as long as the thermal driving strength is less than the order of that of the periodic driving. The power of this result is its simplicity. The surprising accuracy of the time-dependent noise-free geometry for obtaining transition state theory rates in chemical reactions driven by periodic fields reveals the dynamics without requiring the cost of brute-force calculations.

show abstract

A Reversible, Unidirectional Molecular Rotary Motor Driven by Chemical Energy

Cited by 431 publications

References 31 publications

An autonomous chemically fuelled small-molecule motor

An autonomous chemically fuelled small-molecule motor

Bimodal dynamics of mechanically constrained hydrogen bonds revealed by vibrational photon echoes

Chemical reactions induced by oscillating external fields in weak thermal environments

Contact Info

Product

Resources

About