Abstract
Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.
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References
Whitesides, G. M., Mathias, J. P. & Seto, C. T. Molecular self-assembly and nanochemistry—a chemical strategy for the synthesis of nanostructures. Science 254, 1312–1319 (1991).
Lehn, J-M. Supramolecular Chemistry: Concepts and Perspectives (Wiley, 1995).
Hoeben, F. J. M., Jonkheijm, P., Meijer, E. W. & Schenning, A. P. H. J. About supramolecular assemblies of pi-conjugated systems. Chem. Rev. 105, 1491–1546 (2005).
Rowan, S. J., Cantrill, S. J., Cousins, G. R. L., Sanders, J. K. M. & Stoddart, J. F. Dynamic covalent chemistry. Angew. Chem. Int. Ed. 41, 898–952 (2002).
Jin, Y., Yu, C., Denman, R. J. & Zhang, W. Recent advances in dynamic covalent chemistry. Chem. Soc. Rev. 42, 6634–6654 (2013).
Lehn, J-M. Dynamic combinatorial chemistry and virtual combinatorial libraries. Chem. Eur. J. 5, 2455–2463 (1999).
Corbett, P. T. et al. Dynamic combinatorial chemistry. Chem. Rev. 106, 3652–3711 (2006).
Miller, B. L. Dynamic Combinatorial Chemistry in Drug Discovery, Bioorganic Chemistry, and Materials Science (Wiley, 2009).
Lehn, J-M. From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry. Chem. Soc. Rev. 36, 151–160 (2007).
Lehn, J-M. in Constitutional Dynamic Chemistry (ed. Barboiu, M.) 1–32 (Topics in Current Chemistry 332, Springer, 2012).
Fyfe, M. C. T. & Stoddart, J. F. Synthetic supramolecular chemistry. Acc. Chem. Res. 30, 393–401 (1997).
Black, S. P., Sanders, J. K. M. & Stefankiewicz, A. R. Disulfide exchange: exposing supramolecular reactivity through dynamic covalent chemistry. Chem. Soc. Rev. 43, 1861–1872 (2014).
Fuchs, B., Nelson, A., Star, A., Stoddart, J. F. & Vidal, S. B. Amplification of dynamic chiral crown ether complexes during cyclic acetal formation. Angew. Chem. Int. Ed. 42, 4220–4224 (2003).
Cacciapaglia, R., Di Stefano, S. & Mandolini, L. Metathesis reaction of formaldehyde acetals: an easy entry into the dynamic covalent chemistry of cyclophane formation. J. Am. Chem. Soc. 127, 13666–13671 (2005).
Kaiser, G. & Sanders, J. K. M. Synthesis under reversible conditions of cyclic porphyrin dimers using palladium-catalysed allyl transesterification. Chem. Commun. 1763–1764 (2000).
Cordes, E. H. & Jencks, W. P. On the mechanism of Schiff base formation and hydrolysis. J. Am. Chem. Soc. 84, 832–837 (1962).
Layer, R. W. The chemistry of imines. Chem. Rev. 63, 489–510 (1963).
Dayagi, S. & Degani, Y. Methods of Formation of the Carbon–Nitrogen Double Bond 64–83 (Interscience, 1970).
Tauk, L., Schroder, A. P., Decher, G. & Giuseppone, N. Hierarchical functional gradients of pH-responsive self-assembled monolayers using dynamic covalent chemistry on surfaces. Nature Chem. 1, 649–656 (2009).
Bonnett, R. in Carbon–Nitrogen Double Bonds (1970) (ed. Patai, S.) 597–662 (Wiley, 2010).
Belowich, M. E. & Stoddart, J. F. Dynamic imine chemistry. Chem. Soc. Rev. 41, 2003–2024 (2012).
Cote, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).
Korich, A. L. & Iovine, P. M. Boroxine chemistry and applications: a perspective. Dalton Trans. 39, 1423–1431 (2010).
Ciaccia, M., Cacciapaglia, R., Mencarelli, P., Mandolini, L. & Di Stefano, S. Fast transimination in organic solvents in the absence of proton and metal catalysts. A key to imine metathesis catalyzed by primary amines under mild conditions. Chem. Sci. 4, 2253–2261 (2013).
Rue, N. M., Sun, J. L. & Warmuth, R. Polyimine container molecules and nanocapsules. Isr. J. Chem. 51, 743–768 (2011).
Kovaříček, P. & Lehn, J-M. Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes. J. Am. Chem. Soc. 134, 9446–9455 (2012).
Ramström, O. & Lehn J-M. Drug discovery by dynamic combinatorial libraries. Nature Rev. Drug. Discov. 1, 26–36 (2002).
Zhao, D. H. & Moore, J. S. Reversible polymerization driven by folding. J. Am. Chem. Soc. 124, 9996–9997 (2002).
Giuseppone, N. Toward self-constructing materials: a systems chemistry approach. Acc. Chem. Res. 45, 2178–2188 (2012).
Gourdon, A. On-surface covalent coupling in ultrahigh vacuum. Angew. Chem. Int. Ed. 47, 6950–6953 (2008).
Hossain, M. Z. et al. Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. Nature Chem. 4, 305–309 (2012).
Saywell, A., Schwarz, J., Hecht, S. & Grill, L. Polymerization on stepped surfaces: alignment of polymers and identification of catalytic sites. Angew. Chem. Int. Ed. 51, 5096–5100 (2012).
Di Giovannantonio, M. et al. Insight into organometallic intermediate and its evolution to covalent bonding in surface-confined Ullmann polymerization. ACS Nano 7, 8190–8198 (2013).
Binnig, G., Rohrer, H., Gerber, C. & Weibel, E. Surface studies by scanning tunneling microscopy. Phys. Rev. Lett. 49, 57–61 (1982).
Rabe, J. P. & Buchholz, S. Commensurability and mobility in 2-dimensional molecular-patterns on graphite. Science 253, 424–427 (1991).
De Feyter, S. & De Schryver, F. C. Two-dimensional supramolecular self-assembly probed by scanning tunneling microscopy. Chem. Soc. Rev. 32, 139–150 (2003).
Jackson, A. M., Myerson, J. W. & Stellacci, F. Spontaneous assembly of subnanometre-ordered domains in the ligand shell of monolayer-protected nanoparticles. Nature Mater. 3, 330–336 (2004).
MacLeod, J. M., Ivasenko, O., Perepichka, D. F. & Rosei, F. Stabilization of exotic minority phases in a multicomponent self-assembled molecular network. Nanotechnology 18, 424031–424040 (2007).
Ciesielski, A., Schaeffer, G., Petitjean, A., Lehn, J-M. & Samorì, P. STM insight into hydrogen-bonded bicomponent 1D supramolecular polymers with controlled geometries at the liquid–solid interface. Angew. Chem. Int. Ed. 48, 2039–2043 (2009).
Ciesielski, A., Palma, C-A., Bonini, M. & Samorì, P. Towards supramolecular engineering of functional nanomaterials: pre-programming multi-component 2D self-assembly at solid–liquid interfaces. Adv. Mater. 22, 3506–3520 (2010).
Ciesielski, A., Lena, S., Masiero, S., Spada, G. P. & Samorì, P. Dynamers at the solid–liquid interface: controlling the reversible assembly/reassembly process between two highly ordered supramolecular guanine motifs. Angew. Chem. Int. Ed. 49, 1963–1966 (2010).
Ciesielski, A. & Samorì, P. Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces. Nanoscale 3, 1397–1410 (2011).
Grill, L. et al. Nano-architectures by covalent assembly of molecular building blocks. Nature Nanotech. 2, 687–691 (2007).
Hulsken, B. et al. Real-time single-molecule imaging of oxidation catalysis at a liquid–solid interface. Nature Nanotech. 2, 285–289 (2007).
Perepichka, D. F. & Rosei, F. Extending polymer conjugation into the second dimension. Science 323, 216–217 (2009).
Mielke, J. et al. Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulation. J. Phys. Condens. Matter 24, 394013 (2012).
den Boer, D. et al. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface. Nature Chem. 5, 621–627 (2013).
Ghijsens, E, et al. A tale of tails: alkyl chain directed formation of 2D porous networks reveals odd–even effects and unexpected bicomponent phase behavior. ACS Nano 7, 8031–8042 (2013).
Dienstmaier, J. F. et al. Synthesis of well-ordered COF monolayers: surface growth of nanocrystalline precursors versus direct on-surface polycondensation. ACS Nano 5, 9737–9745 (2011).
Dienstmaier, J. F. et al. Isoreticular two-dimensional covalent organic frameworks synthesized by on-surface condensation of diboronic acids. ACS Nano 6, 7234–7242 (2012).
Hu, F. Y. et al. In situ STM investigation of two-dimensional chiral assemblies through Schiff-base condensation at a liquid/solid interface. ACS Appl. Mater. Interfaces 5, 1583–1587 (2013).
Wang, X. Y. et al. Structural motif modulation in 2D supramolecular assemblies of molecular dipolar unit tethered by alkylene spacer. J. Phys. Chem. C 117, 16392–16396 (2013).
Guan, C. Z., Wang, D. & Wan, L. J. Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation. Chem. Commun. 48, 2943–2945 (2012).
Weigelt, S. et al. Covalent interlinking of an aldehyde and an amine on a Au(111) surface in ultrahigh vacuum. Angew. Chem. Int. Ed. 46, 9227–9230 (2007).
Weigelt, S. et al. Surface synthesis of 2D branched polymer nanostructures. Angew. Chem. Int. Ed. 47, 4406–4410 (2008).
Tanoue, R. et al. Thermodynamically controlled self-assembly of covalent nanoarchitectures in aqueous solution. ACS Nano 5, 3923–3929 (2011).
Piot, L., Bonifazi, D. & Samorì, P. Organic reactivity in confined spaces under scanning tunneling microscopy control: tailoring the nanoscale world. Adv. Func. Mater. 17, 3689–3693 (2007).
Stabel, A., Heinz, R., De Schryver, F. C. & Rabe, J. P. Ostwald ripening of 2-dimensional crystals at the solid–liquid interface. J. Phys. Chem. 99, 505–507 (1995).
Samorí, P., Müllen, K. & Rabe, H. P. Molecular-scale tracking of the self-healing of polycrystalline monolayers at the solid–liquid interface. Adv. Mater. 16, 1761–1765 (2004).
Samorí, P., Severin, N., Müllen, K. & Rabe, J. P. Macromolecular fractionation of rod-like polymers at atomically flat solid–liquid interfaces. Adv. Mater. 12, 579–582 (2000).
Cheeseman, J. D., Corbett, A. D., Gleason, J. L. & Kazlauskas, R. J. Receptor-assisted combinatorial chemistry: thermodynamics and kinetics in drug discovery. Chem. Eur. J. 11, 1708–1716 (2005).
Belenguer, A. M., Friscic, T., Day, G. M. & Sanders, J. K. M. Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis. Chem. Sci. 2, 696–700 (2011).
Bonini, M. et al. Competitive physisorption among alkyl-substituted pi-conjugated oligomers at the solid–liquid interface: towards prediction of self-assembly at surfaces from a multicomponent solution. Small 5, 1521–1526 (2009).
Baxter, P. N. W., Lehn, J-M. & Rissanen, K. Generation of an equilibrating collection of circular inorganic copper(I) architectures and solid-state stabilisation of the dicopperhelicate component. Chem. Commun. 1323–1324 (1997).
Acknowledgements
We thank M. Cecchini for enlightening discussions. P.K. acknowledges the Université de Strasbourg for a doctoral fellowship. This work was supported by the European Community through the European Research Council projects SUPRAFUNCTION (GA-257305) and SUPRADAPT (GA-290585), the Agence Nationale de la Recherche through the LabEx project Chemistry of Complex Systems (ANR-10-LABX-0026_CSC) and the International Center for Frontier Research in Chemistry.
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A.C., P.S. and J-M.L. conceived the experiments and designed the study. P.K. participated in the planning of the study and carried out the synthesis and characterization in solution (HPLC, and NMR and mass spectroscopy). M.E.G. and S.H. performed the STM experiments. M.E.G., A.C. and P.S. interpreted the STM data. J-M.L. and P.K. interpreted the chemical data. All authors discussed the results and contributed to the interpretation of data. A.C., P.S. and J-M.L. co-wrote the paper. All authors contributed to editing the manuscript.
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Ciesielski, A., El Garah, M., Haar, S. et al. Dynamic covalent chemistry of bisimines at the solid/liquid interface monitored by scanning tunnelling microscopy. Nature Chem 6, 1017–1023 (2014). https://doi.org/10.1038/nchem.2057
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DOI: https://doi.org/10.1038/nchem.2057
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