The surface-assisted bottom-up fabrication of graphene nanoribbons (GNRs), which consists of the radical polymerization of precursors followed by dehydrogenation, has attracted attention because of the method's ability to control the edges and widths of the resulting ribbon. Although these reactions on a metal surface are believed to be catalytic, the mechanism has remained unknown. Here, we demonstrate ‘conformation-controlled surface catalysis’: the two-zone chemical vapour deposition of a ‘Z-bar-linkage’ precursor, which represents two terphenyl units linked in a ‘Z’ shape, results in the efficient formation of acene-type GNRs with a width of 1.45 nm through optimized cascade reactions. These precursors exhibit flexibility that allows them to adopt chiral conformations with height asymmetry on a Au(111) surface, which enables the production of self-assembled homochiral polymers in a chain with a planar conformation, followed by dehydrogenation via a conformation-controlled mechanism. This is conceptually analogous to enzymatic catalysis and will be useful for the fabrication of new nanocarbon materials.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Communications Open Access 15 May 2018
Nature Communications Open Access 20 July 2017
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
Chen, L., Hernandez, Y., Feng, X. & Müllen, K. From nanographene and graphene nanoribbons to graphene sheets: chemical synthesis. Angew. Chem. Int. Ed. 51, 7640–7654 (2012).
Narita, A., Wang, X.-Y., Feng, X. & Müllen, K. New advances in nanographene chemistry. Chem. Soc. Rev. 44, 6616–6643 (2015).
Yang, L., Park, C.-H., Son, Y.-W., Cohen, M. L. & Louie, S. G. Quasiparticle energies and band gaps in graphene nanoribbons. Phys. Rev. Lett. 99, 186801 (2007).
Son, Y.-W., Cohen, M. L. & Louie, S. G. Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).
Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010).
Zhang, H. et al. On-surface synthesis of rylene-type graphene nanoribbons. J. Am. Chem. Soc. 137, 4022–4025 (2015).
Cai, J. et al. Graphene nanoribbon heterojunctions. Nat. Nanotech. 9, 896–900 (2014).
Chen, Y.-C. et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nat. Nanotech. 10, 156–160 (2015).
Linden, S. et al. Electronic structure of spatially aligned graphene nanoribbons on Au(788). Phys. Rev. Lett. 108, 216801 (2012).
Huang, H. et al. Spatially resolved electronic structures of atomically precise armchair graphene nanoribbons. Sci. Rep. 2, 983 (2012).
Bronner, C. et al. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem. Int. Ed. 52, 4422–4425 (2013).
Sakaguchi, H. et al. Width-controlled sub-nanometer graphene nanoribbon films synthesized by radical-polymerized chemical vapor deposition. Adv. Mater. 26, 4134–4138 (2014).
Ertl, G. Reactions at surfaces: from atoms to complexity (Nobel Lecture). Angew. Chem. Int. Ed. 47, 3524–3535 (2008).
Hammer, B. & Nørskov, J. K. Why gold is the noblest of all the metals. Nature 376, 238–240 (1995).
Björk, J., Stafström, S. & Hanke, F. Zipping up: cooperativity drives the synthesis of graphene nanoribbons. J. Am. Chem. Soc. 133, 14884–14887 (2011).
Blankenburg, S. et al. Intraribbon heterojunction formation in ultranarrow graphene nanoribbons. ACS Nano 6, 2020–2025 (2012).
Treier, M. et al. Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes. Nat. Chem. 3, 61–67 (2011).
Narita, A. et al. Synthesis of structurally well-defined and liquid-phase-processable graphene nanoribbons. Nat. Chem. 6, 126–132 (2014).
Liu, J. et al. Towards cove-edged low band gap graphene nanoribbons. J. Am. Chem. Soc. 137, 6097–6103 (2015).
Magda, G. Z. et al. Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons. Nature 514, 608–611 (2014).
Chen, L., Wang, L. & Beljonne, D. Designing coved graphene nanoribbons with charge carrier mobility approaching that of graphene. Carbon 77, 868–879 (2014).
Garcia-Viloca, M., Gao, J., Karplus, M. & Truhlar, D. G. How enzymes work: analysis by modern rate theory and computer simulations. Science 303, 186–195 (2004).
Fersht, A. Structure and Mechanism in Protein Science Ch. 13 (Freeman, 1999).
Marsh, J. A. & Teichmann, S. A. Structure, dynamics, assembly, and evolution of protein complexes. Annu. Rev. Biochem. 84, 551–575 (2015).
Elemans, J. A. A. W., De Cat, I., Xu, H. & De Feyter, S. Two-dimensional chirality at liquid–solid interfaces. Chem. Soc. Rev. 38, 722–736 (2009).
Fasel, R., Parschau, M. & Ernst, K.-H. Amplification of chirality in two-dimensional enantiomorphous lattices. Nature 439, 449–452 (2006).
Lorenzo, M. O., Baddeley, C. J., Muryn, C. & Raval, R. Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules. Nature 404, 376–379 (2000).
Böhringer, M., Morgenstern, K., Schneider, W.-D. & Berndt, R. Separation of a racemic mixture of two-dimensional molecular clusters by scanning tunneling microscopy. Angew. Chem. Int. Ed. 38, 821–823 (1999).
Chen, Q. & Richardson, N. V. Enantiomeric interactions between nucleic acid bases and amino acids on solid surfaces. Nat. Mater. 2, 324–328 (2003).
Weckesser, J., De Vita, A., Barth, J., Cai, C. & Kern, K. Mesoscopic correlation of supramolecular chirality in one-dimensional hydrogen-bonded assemblies. Phys. Rev. Lett. 87, 096101 (2001).
Okamoto, Y. & Nakano, T. Asymmetric polymerization. Chem. Rev. 94, 349–372 (1994).
Nakano, T. & Okamoto, Y. Synthetic helical polymers: conformation and function. Chem. Rev. 101, 4013–4038 (2001).
Yashima, E. Synthesis and structure determination of helical polymers. Polym. J. 42, 3–16 (2010).
Brintzinger, H. H., Fischer, D., Mülhaupt, R., Rieger, B. & Waymouth, R. M. Stereospecific olefin polymerization with chiral metallocene catalysts. Angew. Chem. Int. Ed. 34, 1143–1170 (1995).
Castonguay, L. A. & Rappé, A. K. Ziegler–Natta catalysis. A theoretical study of the isotactic polymerization of propylene. J. Am. Chem. Soc. 114, 5832–5842 (1992).
Chen, T.-A. & Rieke, R. D. The first regioregular head-to-tail poly (3-hexylthiophene-2,5-diyl) and a regiorandom isopolymer: Ni vs Pd catalysis of 2(5)-bromo-5(2)-(bromozincio)-3-hexylthiophene polymerization. J. Am. Chem. Soc. 114, 10087–10088 (1992).
McCullough, R. D. The chemistry of conducting polythiophenes. Adv. Mater. 10, 93–116 (1998).
Yang, L., Tan, X., Wang, Z. & Zhang, X. Supramolecular polymers: historical development, preparation, characterization, and functions. Chem. Rev. 155, 7196–7239 (2015).
Kang, J. et al. A rational strategy for the realization of chain-growth supramolecular polymerization. Science 347, 646–651 (2015).
Korevaar, P. A. et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012).
Ishida, Y. & Aida, T. Homochiral supramolecular polymerization of an ‘S’-shaped chiral monomer: translation of optical purity into molecular weight distribution. J. Am. Chem. Soc. 124, 14017–14019 (2002).
Guilleme, J. et al. Non-centrosymmetric homochiral supramolecular polymers of tetrahedral subphthalocyanine molecules. Angew. Chem. Int. Ed. 54, 2543–2547 (2015).
Han, P. et al. Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity. ACS Nano 8, 9181–9187 (2014).
Lingenfelder, M. et al. Tracking the chiral recognition of adsorbed dipeptides at the single-molecule level. Angew. Chem. Int. Ed. 46, 4492–4495 (2007).
Reichardt, C., Schroeder, J., Vöhringer, P. & Schwarzer, D. Unravelling the ultrafast photodecomposition mechanism of dibenzoyl peroxide in solution by time-resolved IR spectroscopy. Phys. Chem. Chem. Phys. 10, 1662–1668 (2008).
Matyjaszewski, K. Lifetimes of polystyrene chains in atom transfer radical polymerization. Macromolecules 32, 9051–9053 (1999).
Wang, X. & Dai, H. Etching and narrowing of graphene from the edges. Nat. Chem. 2, 661–665 (2010).
Son, J. G. et al. Sub-10 nm graphene nanoribbon array field-effect transistors fabricated by block copolymer lithography. Adv. Mater. 25, 4723–4728 (2013).
Li, X., Wang, X., Zhang, L., Lee, S. & Dai, H. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 319, 1229–1232 (2008).
Bennett, P. B. et al. Bottom-up graphene nanoribbon field-effect transistors. Appl. Phys. Lett. 103, 253114 (2013).
Abbas, A. N. et al. Deposition, characterization, and thin-film-based chemical sensing of ultra-long chemically synthesized graphene nanoribbons. J. Am. Chem. Soc. 136, 7555–7558 (2014).
This study was supported by Grant-in-Aids for Scientific Research no. 26620101, Innovative Areas ‘Molecular Architectonics’ (2509) and ‘π-Figuration’ (2610), The Ministry of Education Culture, Sports, Science and Technology, Japan; ‘Zero-Emission Energy Research’ of the International Energy Agency, Kyoto University. Super Computer System, Institute for Chemical Research, Kyoto University was used for the calculations. We thank S. Fujita, N. Taira and M. Yano for technical assistance.
The authors declare no competing financial interests.
About this article
Cite this article
Sakaguchi, H., Song, S., Kojima, T. et al. Homochiral polymerization-driven selective growth of graphene nanoribbons. Nature Chem 9, 57–63 (2017). https://doi.org/10.1038/nchem.2614
This article is cited by
Nature Chemistry (2021)
Science China Chemistry (2021)
Nature Chemistry (2020)
Method of preparation of alkylated 1,3-diphenylpropan-2-ones, the components for assembly of graphene nanostructures
Russian Chemical Bulletin (2020)