Abstract
In the last decade many molecular machines with controlled molecular motions have been synthesized. In the present review chapter we will present and discuss our contribution to the field, in particular through some examples of rotating molecular machines that have been designed, synthesized, and studied in our group. After starting by explaining why it is so important to study such machines as single molecules, we will focus on two families of molecular machines, nanovehicles and molecular motors. The first members of the nanovehicle family are molecules with two triptycenes as wheels: the axle and the wheelbarrow. Then come the four-wheel nanocars. Since triptycene wheels are not very mobile on metallic surfaces, alternative wheels with a bowl-shape structure have also been synthesized and studied on surfaces. The molecular motors are built around ruthenium organometallic centers and have a piano-stool geometry with peripheric ferrocenyl groups.
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Abbreviations
- ANR:
-
French national research agency
- ASED+:
-
Atom superposition and electron delocalization
- ATP:
-
Adenosine triphosphate
- CNRS:
-
Centre National de la Recherche Scientifique
- Cp:
-
Cyclopentadienyl
- EG:
-
Electroactive group
- ESQC:
-
Elastic scattering quantum chemistry
- IR:
-
Infrared
- LT:
-
Low temperature
- NC-AFM:
-
Non-contact atomic force microscope
- NMR:
-
Nuclear magnetic resonance
- P3N:
-
Nanosciences, nanotechnologies, and nanosystems program
- PAH:
-
Polycyclic aromatic hydrocarbon
- STM:
-
Scanning tunneling microscope
- THF:
-
Tetrahydrofuran
- UHV:
-
Ultra high vacuum
References
Howe RT, Muller RS, Gabriel KJ, Trimmer WSN (1990) Silicon micromechanics – sensors and actuators on a chip. IEEE Spectrum 27:29
Ishijima A, Harada Y, Kojima H, Funatsu T, Higuchi H, Yanagida T (1994) Single-molecule analysis of the actomyosin motor using nano-manipulation. Biochem Biophys Res Commun 199:1057
Block SM (1997) Real engines of creation. Nature 386:217
Gimzewski JK, Joachim C, Schlittler RR, Langlais V, Tang H, Johannsen I (1998) Rotation of a single molecule within a supramolecular bearing. Science 281:531
Rapenne G (2005) Synthesis of technomimetic molecules: towards rotation control in single molecular machines and motors. Org Biomol Chem 3:1165
Chance JM, Geiger JH, Mislow K (1989) A parity restriction on dynamic gearing immobilizes the rotors in tris(9-triptycyl)germanium chloride and tris(9-triptycyl)cyclopropenium perchlorate. J Am Chem Soc 111:2326
Clayden J, Pink JH (1998) Concerted rotation in a tertiary aromatic amide: towards a simple molecular gear. Angew Chem Int Ed 37:1937
Carella A, Jaud J, Rapenne G, Launay J-P (2003) Technomimetic molecules: synthesis of an organometallic molecular turnstile. Chem Commun 2434
Chiaravalloti F, Gross L, Rieder KH, Stojkovic S, Gourdon A, Joachim C, Moresco F (2007) A rack-and-pinion device at the molecular scale. Nat Mater 6:30
Joachim C, Moresco F, Rapenne G, Meyer G (2002) The design of a nanoscale molecular barrow. Nanotechnology 13:330
Grill L, Rieder KH, Moresco F, Rapenne G, Stojkovic S, Bouju X, Joachim C (2007) Rolling a single molecular wheel at the atomic scale. Nat Nanotechnol 2:95
Jacquot de Rouville H-P, Garbage R, Ample F, Nickel A, Meyer J, Moresco F, Joachim C, Rapenne G (2012) Synthesis and STM imaging of symmetric and dissymmetric ethynyl-bridged dimers of boron-subphthalocyanine bowl-shaped nano-wheels. Chem Eur J 18:8925
Nickel A, Meyer J, Ohmann R, Jacquot de Rouville H-P, Rapenne G, Joachim C, Cuniberti G, Moresco F (2012) STM manipulation of boron-subphthalocyanine nano-wheel dimers on Au(111). J Phys Condens Matter 24:404001
Chu P-LE, Wang L-Y, Khatua S, Kolomeisky AB, Link S, Tour JM (2013) Synthesis and single-molecule imaging of highly mobile adamantane-wheeled nanocars. ACS Nano 7:35
Jimenez-Bueno G, Rapenne G (2003) Technomimetic molecules: synthesis of a molecular wheelbarrow. Tetrahedron Lett 44:6261
Rapenne G, Jimenez-Bueno G (2007) Molecular machines: synthesis and characterization of two prototypes of molecular wheelbarrows. Tetrahedron 63:7018
Grill L, Rieder KH, Moresco F, Jimenez-Bueno G, Wang C, Rapenne G, Joachim C (2005) Imaging of a molecular wheelbarrow by scanning tunneling microscopy. Surf Sci 584:153
Shirai Y, Osgood AJ, Zhao Y, Kelly KF, Tour JM (2005) Directional control in thermally driven single-molecule nanocars. Nano Lett 5:2330
Joachim C, Rapenne G (2013) Molecule concept nanocars: chassis, wheels and motors? ACS Nano 7:11
Vives G, Tour JM (2009) Synthesis of single-molecule nanocars. Acc Chem Res 42:473
Kudernac T, Ruangsupapichat N, Parschau M, Maci B, Katsonis N, Harutyunyan SR, Ernst K-H, Feringa BL (2011) Electrically driven directional motion of a four-wheeled molecule on a metal surface. Nature 479:208
Jacquot de Rouville H-P, Garbage R, Cook RE, Pujol AR, Sirven AM, Rapenne G (2012) Synthesis of polycyclic aromatic hydrocarbon-based nanovehicles equipped with triptycene wheels. Chem Eur J 18:3023
Leigh DA, Wong JKY, Dehez F, Zerbetto F (2003) Unidirectional rotation in a mechanically interlocked molecular rotor. Nature 424:174
Kottas GS, Clarke LI, Horinek D, Michl J (2005) Artificial molecular rotors. Chem Rev 105:1281
Kelly TR, Silva HD, Silva RA (1999) Unidirectional rotary motion in a molecular system. Nature 401:150
Koumura N, Zijlstra RWJ, van Delden RA, Harada N, Feringa BL (1999) Light-driven monodirectional molecular rotor. Nature 401:152
Ruangsupapichat N, Pollard MM, Harutyunyan SR, Feringa BL (2011) Reversing the direction in a light-driven rotary molecular motor. Nat Chem 3:53
Kay ER, Leigh DA, Zerbetto F (2007) Synthetic molecular motors and mechanical machines. Angew Chem Int Ed 46:72
Vives G, Jacquot de Rouville H-P, Carella A, Launay J-P, Rapenne G (2009) Prototypes of molecular motors based on star-shaped organometallic ruthenium complexes. Chem Soc Rev 38:1551
Perera UGE, Ample F, Echeverria J, Kersell H, Zhang Y, Vives G, Rapenne G, Joachim C, Hla S-W (2013) Clockwise or counterclockwise unidirectional step-by-step rotation of a single molecular motor. Nat Nanotechnol 8:46
Tierney HL, Murphy CJ, Jewell AD, Baber AE, Iski EV, Khodaverdian HY, McGuire AF, Klebanov N, Sykes ECH (2011) Experimental demonstration of a single-molecule electric motor. Nat Nanotechnol 6:625
Joachim C, Gimzewski JK (2001) Single molecular rotor at the nanoscale. Struct Bond 99:1
Manzano C, Soe W-H, Wong HS, Ample F, Gourdon A, Chandrasekhar N, Joachim C (2009) Step-by-step rotation of a molecule-gear mounted on an atomic-scale axis. Nat Mater 8:576
Moresco F, Meyer G, Rieder KH, Tang H, Gourdon A, Joachim C (2001) Recording intramolecular mechanics during the manipulation of a large molecule. Phys Rev Lett 87:088302
Loppacher C, Guggisberg M, Pfeiffer O, Meyer E, Bammerlin M, Lüthi R, Schlittler RR, Gimzewski JK, Tang H, Joachim C (2003) Direct determination of the energy required to operate a single molecule switch. Phys Rev Lett 90:066107
Garcia EJ, Sniegowski JJ (1995) Surface micromachined microengine. Sens Actuators A Phys 48:203
Jun YJ, Ah CS, Kim S, Yun WS, Park BC, Ha DH (2007) Manipulation of freestanding Au nanogears using an atomic force microscope. Nanotechnology 18:505304
Deng J, Troadec C, Ample F, Joachim C (2011) Fabrication and manipulation of solid-state SiO2 nano-gears on a gold surface. Nanotechnology 22:275307
Toyota S (2010) Rotational isomerism involving acetylene carbon. Chem Rev 110:5398
Palmino F, Makoudi Y, Duverger E, Arab M, Chérioux F, Rapenne G, Ample F, Bouju X (2008) Self-alignment of organic molecular lines at room temperature by template effect of pre-structured Sm/Si(111)-8x2 interface. Chem Phys Chem 9:1437
Bouju X, Chérioux F, Coget S, Rapenne G, Palmino F (2013) Directional molecular sliding at room temperature on a silicon runway. Nanoscale 5:7005
Walker JF (1998) ATP synthesis by rotary catalysis (Nobel lecture). Angew Chem Int Ed 37:2308
Carella A, Rapenne G, Launay J-P (2005) Design and synthesis of the active part of a potential molecular rotary motor. New J Chem 29:288
Park H, Park J, Lim AKL, Anderson EH, Alivisatos AP, McEuen PL (2000) Nanomechanical oscillations in a single-C60 transistor. Nature 407:57
Trofimenko S (1999) Scorpionates: the coordination chemistry of polypyrazolylborate ligands. Imperial College Press, London
Astruc D (2000) Electron and proton reservoir complexes: thermodynamic basis for C−H activation and applications in redox and dendrimer chemistry. Acc Chem Res 33:287
Broadley K, Lane GA, Connelly NG, Geiger WE (1983) Electrochemical routes to paramagnetic dinuclear and mononuclear palladium π complexes stabilized by the pentaphenylcyclopentadienyl ligand. J Am Chem Soc 105:2486
Carella A, Launay J-P, Poteau R, Rapenne G (2008) Synthesis and reactivity of penta(4-halogenophenyl)cyclopentadienyl hydrotris (indazolyl)borate ruthenium(II) complexes: rotation-induced Fosbury flop in an organometallic molecular turnstile. Chem Eur J 14:8147
Vives G, Carella A, Launay J-P, Rapenne G (2008) The chemistry of 1,2,3,4,5-pentaphenylcyclopentadienyl hydrotris(indazolyl)borate ruthenium(II) complexes, building blocks for the construction of potential organometallic molecular motors. Coord Chem Rev 252:1451
Connelly NG, Manners I (1989) Reduction–oxidation properties of organotransition-metal complexes. Part 29. Pentaphenylcyclopentadienyl complexes of ruthenium. J Chem Soc Dalton Trans 283
Carella A, Vives G, Cox T, Jaud J, Rapenne G, Launay J-P (2006) Synthesis of new tripodal tri-functionalized hydrotris(indazol-1-yl)borate ligands and X-ray structure of their ruthenium cyclopentadiene complexes. Eur J Inorg Chem 980
King AO, Negishi E, Villani FJ, Silveira A (1978) A general synthesis of terminal and internal arylalkynes by the palladium-catalyzed reaction of alkynylzinc reagents with aryl halides. J Org Chem 43:358
Carella A, Coudret C, Guirado G, Rapenne G, Vives G, Launay J-P (2007) Electron-triggered motions in technomimetic molecules. Dalton Trans 177
Vives G, Sistach S, Carella A, Launay J-P, Rapenne G (2006) Synthesis of triester-functionalized molecular motors incorporating bis-acetylide trans-platinum insulating fragments. New J Chem 30:1429
Vives G, Gonzalez A, Jaud J, Launay J-P, Rapenne G (2007) Synthesis of molecular motors incorporating bicyclo[2-2-2]octane insulating fragments. Chem Eur J 13:5622
Vives G, Rapenne G (2008) Directed synthesis of symmetric and dissymmetric molecular motors built around a ruthenium cyclopentadienyl tris(indazolyl)borate complex. Tetrahedron 64:11462
Vives G, Rapenne G (2006) Breaking the symmetry in the molecular motor family: synthesis of a dissymetrized pentaphenyl cyclopentadienyl ligand and its ruthenium trisindazolylborate complex. Tetrahedron Lett 47:8741
Walker SD, Barder TE, Martinelli JR, Buchwald SL (2004) A rationally designed universal catalyst for Suzuki–Miyaura coupling processes. Angew Chem Int Ed 43:1871
Davis AP (1998) Tilting at windmills? The second law survives. Angew Chem Int Ed 37:909
Mandl CP, König B (2004) Chemistry in motion—unidirectional rotating molecular motors. Angew Chem Int Ed 43:1622
Jacquot de Rouville H-P, Vives G, Tur E, Crassous J, Rapenne G (2009) Synthesis and analytical resolution of chiral pyrazoles derived from dihydrocarvone. New J Chem 33:293
Acknowledgements
This work was supported by the CNRS, the Université Paul Sabatier (Toulouse), the Institut Universitaire de France, the European Union, and the ANR P3N (AUTOMOL project no. ANR 09-NANO-040). We are also grateful to the researchers who participated in all the work discussed here and whose names appear in the list of references.
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Rapenne, G., Joachim, C. (2014). Single Rotating Molecule-Machines: Nanovehicles and Molecular Motors. In: Credi, A., Silvi, S., Venturi, M. (eds) Molecular Machines and Motors. Topics in Current Chemistry, vol 354. Springer, Cham. https://doi.org/10.1007/128_2013_510
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DOI: https://doi.org/10.1007/128_2013_510
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