Abstract
The formation of supramolecular rotor-type systems on surfaces under ambient conditions is discussed. We present in detail the assembly of a rotor on a gold surface from solution, where the surface acts as a stator, a pyridyl containing thiol acts as the axle, and a C4 symmetrical porphyrin bearing “paddle-like” arms is the intended rotator. The effective non-covalent attachment of the rotator to the axle is achieved instantly in solution. However, when the axle forms part of a self-assembled monolayer (SAM), the complex formation is practically negated if the SAM’s organization is not appropriate. Thus, the SAM formed on gold by the pyridyl thiol subject of this study does not bind the rotator part of the system—a zinc(II)porphyrin bearing four biphenyl moieties. This negative allosteric surface effect can be overturned by combining the pyridyl thiol with dodecanethiol: the resulting mixed SAM contains pyridyl groups which are oriented quasi-perpendicular to the surface and are therefore available for binding. The difference in the surface organization is achieved using only 1 part in 10 of the alkanethiol (which forms small ordered domains alone). This dramatic effect may find use in other areas where SAMs are used as template layers because the capacity for the surface-anchored ligand to bind solution-borne compounds is affected by its orientation. Exposure of this mixed monolayer to a solution of the zinc(II)porphyrin results in attachment of this rotator component to the surface, which was imaged by scanning tunnelling microscopy (STM). Alternatively, formation of the axle–rotator complex in solution followed by chemisorption of this supramolecular object to the metal surface leads (in places) to a dense layer of the rotators. The presence of the porphyrin was confirmed by mass spectrometry. The results show how the bottom-up route employed can influence the arrangement of ligating moieties in a monolayer, provide a protocol for the preparation of sparse and dense layers of rotors on surfaces, and thereby help plot the road map to the bottom-up creation of surface-based molecular machines based on interconnected rotors.
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References
Koepf, M., Cherioux, F., Wytko, J.A., Weiss, J.: 1D and 3D surface-assisted self-organization. Coord. Chem. Rev. 256, 2872–2892 (2012). doi:10.1016/j.ccr.2012.05.039
Slingenbergh, W., de Boer, S.K., Cordes, T., Browne, W.R., Feringa, B.L., Hoogenboom, J.P., De Hosson, J.T.M., van Dorp, W.F.: Selective functionalization of tailored nanostructures. ACS Nano 6, 9214–9220 (2012). doi:10.1021/nn303571p
Biswas, A., Bayer, I.S., Biris, A.S., Wang, T., Dervishi, E., Faupel, F.: Advances in top-down and bottom-up surface nanofabrication: techniques, applications and future prospects. Adv. Colloid Interface Sci. 170, 2–27 (2012). doi:10.1016/j.cis.2011.11.001
Fabiano, S., Pignataro, B.: Selecting speed-dependent pathways for a programmable nanoscale texture by wet interfaces. Chem. Soc. Rev. 41, 6859–6873 (2012). doi:10.1039/c2cs35074b
Bakewell, D.J.G., Nicolau, D.V.: Protein linear molecular motor-powered nanodevices. Aust. J. Chem. 60, 314–332 (2007). doi:10.1071/CH06456
Schaap, I.A.T., Carrasco, C., de Pablo, P.J., Schmidt, C.F.: Kinesin Walks the line: single motors observed by atomic force microscopy. Biophys. J. 100, 2450–2456 (2011). doi:10.1016/j.bpj.2011.04.015
Boyle, M.M., Smaldone, R.A., Whalley, A.C., Ambrogio, M.W., Botros, Y.Y., Stoddart, J.F.: Mechanised materials. Chem. Sci. 2, 204–210 (2011). doi:10.1039/c0sc00453g
Sauvage, J.-P.: Transition metal-containing rotaxanes and catenanes in motion: toward molecular machines and motors. Acc. Chem. Res. 31, 611–619 (1998). doi:10.1021/ar960263r
Browne, W.R., Feringa, B.L.: Making molecular machines work. Nat. Nanotech. 1, 25–35 (2006). doi:10.1038/nnano.2006.45
Balzani, V., Credi, A., Venturi, M.: Molecular machines working on surfaces and at interfaces. ChemPhysChem 9, 202–220 (2008). doi:10.1002/cphc.200700528
Chiang, P.-T., Mielke, J., Godoy, J., Guerrero, J.M., Alemany, L.B., Villagómez, C.J., Saywell, A., Grill, L., Tour, J.M.: Toward a light-driven motorized nanocar: synthesis and initial imaging of single molecules. ACS Nano 6, 592–597 (2012). doi:10.1021/nn203969b
Chiaravalotti, F., Gross, L., Rieder, K.-H., Stojkovic, S.M., Gourdon, A., Joachim, C., Moresco, F.: A rack-and-pinion device at the molecular scale. Nat. Mater. 6, 30–33 (2007). doi:10.1038/nmat1802
Manzano, C., Soe, W.-H., Wong, H.S., Ample, F., Gourdon, A., Chandrasekhar, N., Joachim, C.: Step-by-step rotation of a molecule-gear mounted on an atomic-scale axis. Nat. Mater. 8, 576–579 (2009). doi:10.1038/NMAT2467
Gimzewski, J.K., Joachim, C., Schlittler, R.R., Langlais, V., Tang, H., Johannsen, I.: Rotation of a single molecule within a supramolecular bearing. Science 281, 531–533 (1998). doi:10.1126/science.281.5376.531
Tanaka, H., Ikeda, T., Takeuchi, M., Sada, K., Shinkai, S., Kawai, T.: Molecular rotation in self-assembled multidecker porphyrin complexes. ACS Nano 5, 9575–9582 (2011). doi:10.1021/nn203773p
Yoshimoto, S., Honda, Y., Ito, O., Itaya, K.: Supramolecular pattern of fullerene on 2D bimolecular “chessboard” consisting of bottom-up assembly of porphyrin and phthalocyanine molecules. J. Am. Chem. Soc. 130, 1085–1092 (2008). doi:10.1021/ja077407p
Kottas, G.S., Clarke, L.I., Horinek, D., Michl, J.: Artificial molecular rotors. Chem. Rev. 105, 1281–1376 (2005). doi:10.1021/cr0300993
Tierney, H.L., Murphy, C.J., Jewell, A.D., Baber, A.E., Iski, E.V., Khodaverdian, H.Y., McGuire, A.F., Klebanov, N., Sykes, E.C.H.: Experimental demonstration of a single-molecule electric motor. Nat. Nanotech. 6, 625–629 (2011). doi:10.1038/NNANO.2011.142
Perera, U.G.E., Ample, F., Kersell, H., Zhang, Y., Vives, G., Echeverria, J., Grisolia, M., Rapenne, G., Joachim, C., Hla, S.W.: Controlled clockwise and anticlockwise rotational switching of a molecular motor. Nat. Nanotech. 8, 46–51 (2013). doi:10.1038/NNANO.2012.218
Puigmartí-Luis, J., Saletra, W.J., González, A., Amabilino, D.B., Pérez-García, L.: Bottom-up assembly of a surface-anchored supramolecular rotor enabled using a mixed self-assembled monolayer and pre-complexed components. Chem. Commun. 50, 82–84 (2014). doi:10.1039/C3CC44794D
Vogel, G.C., Beckmann, B.A.: Binding of pyridine to the phenyl-substituted derivatives of zinc tetraphenylporphine. Inorg. Chem. 15, 483–484 (1976). doi:10.1021/ic50156a054
Mamardashvili, G.M., Kulikova, O.M.: The effect of a solvent on complexation of Zn porphyrinates with pyridine. Russ. J. Coord. Chem. 32, 756–760 (2006). doi:10.1134/S1070328406100101
Da Cruz, F., Driaf, K., Berthier, C., Lameille, J.-M., Armand, F.: Study of a self-assembled porphyrin monomolecular layer obtained by metal complexation. Thin Solid Films 349, 155–161 (1999). doi:10.1016/S0040-6090(99)00169-8
Ferreira, Q., Alcácer, L., Morgado, J.: Stepwise preparation and characterization of molecular wires made of zinc octaethylporphyrin complexes bridged by 4,4′-bipyridine on HOPG. Nanotechnology 22, 435604 (7p) (2011). doi:10.1088/0957-4484/22/43/435604
Dreas-Wlodarczak, A., Müllneritsch, M., Juffmann, T., Cioffi, C., Arndt, M., Mayor, M.: Immobilization of zinc porphyrin complexes on pyridine-functionalized glass surfaces. Langmuir 26, 10822–10826 (2010). doi:10.1021/la100638u
Salassa, G., Coenen, M.J.J., Wezenberg, S.J., Hendriksen, B.L.M., Speller, S., Elemans, J.A.A.W., Kleij, A.W.: Extremely strong self-assembly of a bimetallic salen complex visualized at the single-molecule level. J. Am. Chem. Soc. 134, 7186–7192 (2012). doi:10.1021/ja3030802
Ikeda, M., Takeuchi, M., Shinkai, S., Tani, F., Naruta, Y.: Synthesis of new diaryl-substituted triple-decker and tetraaryl-substituted double-decker lanthanum(III) porphyrins and their porphyrin ring rotational speed as compared with that of double-decker cerium(IV) porphyrins. Bull. Chem. Soc. Jpn 74, 739–746 (2001). doi:10.1246/bcsj.74.739
Otsuki, J., Kawaguchi, S., Yamakawa, T., Asakawa, M., Miyake, K.: Arrays of double-decker porphyrins on highly oriented pyrolytic graphite. Langmuir 22, 5708–5715 (2006). doi:10.1021/la0608617
Ghiggino, K.P., Hutchison, J.A., Langford, S.J., Latter, M.J., Lee, M.A.P., Lowenstern, P.R., Scholes, C., Takezaki, M., Wilman, B.E.: Porphyrin-based molecular rotors as fluorescent probes of nanoscale environments. Adv. Func. Mater. 17, 805–813 (2007). doi:10.1002/adfm.200600948
Guenet, A., Graf, E., Kyritsakas, N., Hosseini, M.W.: Porphyrin-based switchable molecular turnstiles. Chem. Eur. J. 17, 6443–6452 (2011). doi:10.1002/chem.201100057
Cnossen, A., Hou, L., Pollard, M.M., Wesenhagen, P.V., Browne, W.R., Feringa, B.L.: Driving unidirectional molecular rotary motors with visible light by intra- and intermolecular energy transfer from palladium porphyrin. J. Am. Chem. Soc. 134, 17613–17619 (2012). doi:10.1021/ja306986g
Otsuki, J., Komatsu, Y., Kobayashi, D., Asakawa, M., Miyake, K.: Rotational libration of a double-decker porphyrin visualized. J. Am. Chem. Soc. 132, 6870–6871 (2010). doi:10.1021/ja907077e
Yan, S.C., Ding, Z.J., Xie, N., Gong, H.Q., Sun, Q., Guo, Y., Shan, X.Y., Meng, S., Lu, X.H.: Turning on and off the rotational oscillation of a single porphine molecule by molecular charge state. ACS Nano 6, 4132–4136 (2012). doi:10.1021/nn301099m
Lensen, D., Elemans, J.A.A.W.: Artificial molecular rotors and motors on surfaces: STM reveals and triggers. Soft Matter 8, 9053–9063 (2012). doi:10.1039/c2sm26235e
Widrig, C.A., Alves, C.A., Porter, M.D.: Scanning tunnelling microscopy of ethanethiolate and normal-octadecanethiolate monolayers spontaneously adsorbed on gold surfaces. J. Am. Chem. Soc. 113, 2805–2810 (1991). doi:10.1021/ja00008a001
Vericat, C., Vela, M.E., Salvarezza, R.C.: Self-assembled monolayers of alkanethiols on Au(111): surface structures, defects and dynamics. Phys. Chem. Chem. Phys. 7, 3258–3268 (2005). doi:10.1039/b505903h
Silien, C., Buck, M., Goretzki, G., Lahaye, D., Champness, N.R., Weidner, T., Zharnikov, M.: Self-assembly of a pyridine-terminated thiol monolayer on Au(111). Langmuir 25, 959–967 (2009). doi:10.1021/la802966s
Tao, Y.-T., Wu, Ch-Ch., Eu, J.-Y., Lin, W.-L.: Structure evolution of aromatic-derivatized thiol monolayers on evaporated gold. Langmuir 13, 4018–4023 (1997). doi:10.1021/la9700984
Pace, G., Petitjean, A., Lalloz-Vogel, M.-N., Harrowfield, J., Lehn, J.-M., Samorì, P.: Subnanometer-resolved patterning of bicomponent self-assembled monolayers on Au(111). Angew. Chem. Int. Ed. 47, 2484–2488 (2008). doi:10.1002/anie.200704731
Chen, S., Li, L., Boozer, C.L., Jiang, S.: Controlled chemical and structural properties of mixed self-assembled monolayers of alkanethiols on Au(111). Langmuir 16, 9287–9293 (2000). doi:10.1021/la000417i
Wan, L.-J., Hara, Y., Noda, H., Osawa, M.: Dimerization of sulfur headgroups in 4-mercaptopyridine self-assembled monolayers on Au(111) studied by scanning tunneling microscopy. J. Phys. Chem. B 102, 5943–5946 (1998). doi:10.1021/jp981218z
Penon, O., Marsico, F., Santucci, D., Rodríguez, L., Amabilino, D.B., Pérez-García, L.: Multiply biphenyl substituted zinc(II)porphyrin and phthalocyanine as components for molecular materials. J. Porphyrins Phthalocyanines 16, 1293–1302 (2012). doi:10.1142/S1088424612501453
Baber, A.E., Tierney, H.L., Sykes, E.C.H.: A quantitative single-molecule study of thioether molecular rotors. ACS Nano 2, 2385–2391 (2008). doi:10.1021/nn800497y
Coskun, A., Banaszak, M., Astumian, R.D., Stoddart, J.F., Grzybowski, B.A.: Great expectations: can artificial molecular machines deliver on their promise? Chem. Soc. Rev. 41, 19–30 (2012). doi:10.1039/c1cs15262a
von Delius, M., Leigh, D.A.: Walking molecules. Chem. Soc. Rev. 40, 3656–3676 (2011). doi:10.1039/c1cs15005g
Penon, O., Moro, A.J., Santucci, D., Amabilino, D.B., Lima, J.C., Pérez-García, L., Rodríguez, L.: Molecular recognition of aliphatic amines by luminescent Zn-porphyrins. Inorg. Chim. Acta 417, 222–229 (2014). doi:10.1016/j.ica.2013.12.028
Acknowledgments
The research reported here was supported by the MINECO, Spain (projects CTQ2010-16339 and TEC2011-29140-C03-02), and the DGR, Catalonia (Project 2009 SGR 158). The authors acknowledge warmly Dr. Daniel Ruiz-Molina for the loan of the STM head. JPL thanks the MINECO for a Ramón y Cajal contract (RYC-2011-08071).
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Puigmartí-Luis, J., Saletra, W.J., González, A., Pérez-García, L., Amabilino, D.B. (2015). Assembling Supramolecular Rotors on Surfaces Under Ambient Conditions. In: Joachim, C., Rapenne, G. (eds) Single Molecular Machines and Motors. Advances in Atom and Single Molecule Machines. Springer, Cham. https://doi.org/10.1007/978-3-319-13872-5_8
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