Molecular analogues of a variety of mechanical devices such as shuttles, brakes, unidirectional rotors and tweezers have been created1,2,3,4,5,6,7,8,9,10,11. But these ‘molecular machines’ have not yet been used to mechanically manipulate a second molecule in a controlled and reversible manner. Here we show that light-induced scissor-like conformational changes of one molecule5 can give rise to mechanical twisting of a non-covalently bound guest molecule. To realize this coupling of molecular motions, we use a previously designed system5: a ferrocene moiety with an azobenzene strap, each end of which is attached to one of the two cyclopentadienyl rings of the ferrocene unit, acts as a pivot so that photoisomerization of the strap rotates the ferrocene rings relative to each other and thereby also changes the relative position of two ‘pedal’ moieties attached to the ferrocene rings. We translate this effect into intermolecular coupling of motion by endowing the pedals with binding sites, which allow the host system to form a stable complex with a bidentate rotor molecule. Using circular dichroism spectroscopy, we show that the photoinduced conformational changes of the host are indeed transmitted and induce mechanical twisting of the rotor molecule. This design concept, which significantly extends the successful coupling of motion beyond the intramolecular level seen in synthetic allosteric receptors12, might allow for the remote control of molecular events in larger interlocked molecular systems.
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Kinbara, K. & Aida, T. Toward intelligent molecular machines: directed motions of biological and artificial molecules and assemblies. Chem. Rev. 105, 1377–1400 (2005)
Collin, J.-P., Dietrich-Buchecker, C., Gaviña, P., Jimenez-Molero, M. C. & Sauvage, J.-P. Shuttles and muscles: linear molecular machines based on transition metals. Acc. Chem. Res. 34, 477–487 (2001)
Balzani, V., Credi, A., Raymo, F. M. & Stoddart, J. F. Artificial molecular machines. Angew. Chem. Int. Edn Engl. 39, 3348–3391 (2000)
Badjic, J. D., Balzani, V., Credi, A., Silvi, S. & Stoddart, J. F. A molecular elevator. Science 303, 1845–1849 (2004)
Muraoka, T., Kinbara, K., Kobayashi, Y. & Aida, T. Light-driven open–close motion of chiral molecular scissors. J. Am. Chem. Soc. 125, 5612–5613 (2003)
Ishii, D. et al. Chaperonin-mediated stabilization and ATP-triggered release of semiconductor nanoparticles. Nature 423, 628–632 (2003)
Leigh, D. A., Wong, J. K. Y., Dehez, F. & Zerbetto, F. Unidirectional rotation in a mechanically interlocked molecular rotor. Nature 424, 174–179 (2003)
Tashiro, K., Konishi, K. & Aida, T. Metal bisporphyrinate double-decker complexes as redox-responsive rotating modules. Studies on ligand rotation activities of the reduced and oxidized forms using chirality as a probe. J. Am. Chem. Soc. 122, 7921–7926 (2000)
Kelly, T. R., De Silva, H. & Silva, R. A. Unidirectional rotary motion in a molecular system. Nature 401, 150–152 (1999)
Koumura, N., Zijlstra, R. W. J., van Delden, R. A., Harada, N. & Feringa, B. L. Light-driven monodirectional molecular rotor. Nature 401, 152–155 (1999)
Shinkai, S., Ogawa, T., Nakaji, T., Kusano, Y. & Manabe, O. Photocontrolled extraction ability of azobenzene-bridged azacrown ether. Tetrahedr. Lett. 20, 4569–4572 (1979)
Rebek, J. & Wattley, R. V. Allosteric effects: remote control of ion transport selectivity. J. Am. Chem. Soc. 102, 4853–4854 (1980)
Guo, Y.-M., Oike, H. & Aida, T. Chiroptical transcription of helical information through supramolecular harmonization with dynamic helices. J. Am. Chem. Soc. 126, 716–717 (2004)
Borovkov, V. V., Hembury, G. A. & Inoue, Y. Origin, control, and application of supramolecular chirogenesis in bisporphyrin-based systems. Acc. Chem. Res. 37, 449–459 (2004)
Huang, X. et al. Absolute configurational assignments of secondary amines by CD-sensitive dimeric zinc porphyrin host. J. Am. Chem. Soc. 124, 10320–10335 (2002)
Harada, N., Chen, S. L. & Nakanishi, K. Quantitative definition of exciton chirality and the distant effect in the exciton chirality method. J. Am. Chem. Soc. 97, 5345–5352 (1975)
Hanazaki, I. & Akimoto, H. Optical rotatory power of 2,2′-dihydroxy-1,1′-binaphthyl and related compounds. J. Am. Chem. Soc. 94, 4102–4106 (1972)
Tamai, N. & Miyasaka, H. Ultrafast dynamics of photochromic system. Chem. Rev. 100, 1875–1890 (2000)
Spörlein, S. et al. Ultrafast spectroscopy reveals subnanosecond peptide conformational dynamics and validates molecular dynamics simulation. Proc. Natl Acad. Sci. USA 99, 7998–8002 (2002)
Wachtveitl, J. et al. Ultrafast conformational dynamics in cyclic azobenzene peptides of increased flexibility. Biophys. J. 86, 2350–2362 (2004)
Gardner, A. B., Howard, J., Waddington, T. C., Richardson, R. M. & Tomkinson, J. The dynamics of ring rotation in ferrocene, nickelocene, and ruthenocene by incoherent quasi-elastic neutron scattering. Chem. Phys. 57, 453–460 (1981)
Stephenson, D. S. & Binsch, G. Improved algorism for the computation of exchange-broadened NMR bandshapes. J. Magn. Reson. 30, 625–626 (1978)
T.M. thanks the JSPS Young Scientist Fellowship. This research was partially supported by the Ministry of Education, Science, Sports and Culture, Grant-in-Aid for Scientific Research on Priority Areas ‘Life-Surveyors’ (to K.K.). We thank Y. Casta and S. Nara for cooperation in synthesis, and N. Tamai and M. Irie for discussion on photophysics.
Reprints and permissions information is available at npg.nature.com/reprintsandpermissions. The authors declare no competing financial interests.
This file contains the Supplementary Methods (experimental details for synthesis and measurements) and Supplementary Figures 1-12. (PDF 1867 kb)
This movie represents computer-generated 3D molecular models of 2otrans-1 and 2ocis-1 viewed from various angles. (MOV 9094 kb)
About this article
Cite this article
Muraoka, T., Kinbara, K. & Aida, T. Mechanical twisting of a guest by a photoresponsive host. Nature 440, 512–515 (2006) doi:10.1038/nature04635
Physical Chemistry Chemical Physics (2019)
Water-mediated deracemization of a bisporphyrin helicate assisted by diastereoselective encapsulation of chiral guests
Nature Communications (2019)
(Nano)mechanical Motion Triggered by Metal Coordination: from Functional Devices to Networked Multicomponent Catalytic Machinery
Chemical Reviews (2019)
Azobenzene-Bridged Expanded “Texas-sized” Box: A Dual-Responsive Receptor for Aryl Dianion Encapsulation
Journal of the American Chemical Society (2019)
Dalton Transactions (2019)