Nanometre-sized carbon materials consisting of benzene units oriented in unique geometric patterns, hereafter named nanocarbons, conduct electricity, absorb and emit light, and exhibit interesting magnetic properties. Spherical fullerene C60, cylindrical carbon nanotubes and sheet-like graphene are representative forms of nanocarbons, and theoretical simulations have predicted several exotic 3D nanocarbon structures. At present, synthetic routes to nanocarbons mainly lead to mixtures of molecules with a range of different structures and properties, which cannot be easily separated or refined into pure forms. Some researchers believe that it is impossible to synthesize these materials in a precise manner. Obtaining ‘pure’ nanocarbons is a great challenge in the field of nanocarbon science, and the construction of structurally uniform nanocarbons, ideally as single molecules, is crucial for the development of functional materials in nanotechnology, electronics, optics and biomedical applications. This Review highlights the organic chemistry approach — more specifically, bottom-up construction with atomic precision — that is currently the most promising strategy towards this end.
Your institute does not have access to this article
Open Access articles citing this article.
Nature Synthesis Open Access 19 May 2022
Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation
Nature Communications Open Access 03 May 2022
Three-dimensional acetylenic modified graphene for high-performance optoelectronics and topological materials
npj Computational Materials Open Access 16 July 2021
Subscribe to Journal
Get full journal access for 1 year
only $8.25 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.
Kroto, H. W., Heath, J. R., O'Brien, S. C., Curl, R. F. & Smalley, R. E. C60: buckminsterfullerene. Nature 318, 162–163 (1985).
Iijima, S. Helical microtubules of graphitic carbon. Nature 354, 56–58 (1991).
Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).
Terrones, H., Lv, R., Terrones, M. & Dresselhaus, M. S. The role of defects and doping in 2D graphene sheets and 1D nanoribbons. Rep. Prog. Phys. 75, 062501 (2012).
Dresselhaus, M., Dresselhaus, G. & Avouris, P. (eds) Carbon Nanotubes: Synthesis, Properties and Applications (Springer, 2001).
Bachilo, S. M. et al. Narrow (n, m)-distribution of single-walled carbon nanotubes grown using a solid supported catalyst. J. Am. Chem. Soc. 125, 11186–11187 (2003).
Chiang, W.-H. & Sankaran, R. M. Linking catalyst composition to chirality distributions of as-grown single-walled carbon nanotubes by tuning NixFe1−x nanoparticles. Nat. Mater. 8, 882–886 (2009).
Kato, T. & Hatakeyama, R. Direct growth of short single-walled carbon nanotubes with narrow-chirality distribution by time-programmed plasma chemical vapor deposition. ACS Nano 4, 7395–7400 (2010).
Tu, X., Manohar, S., Jagota, A. & Zheng, M. DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes. Nature 460, 250–253 (2009).
Han, M. Y., Ozyilmaz, B., Zhang, Y. & Kim, P. Energy band-gap engineering of graphene nanoribbons. Phys. Rev. Lett. 98, 206805 (2007).
Chen, Z., Lin, Y.-M., Rooks, M. J. & Avouris, P. Graphene nano-ribbon electronics. Phys. E 40, 228–232 (2007).
Kosynkin, D. V. et al. Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature 458, 872–876 (2009).
Jiao, L., Zhang, L., Wang, X., Diankov, G. & Dai, H. Narrow graphene nanoribbons from carbon nanotubes. Nature 458, 877–880 (2009).
Avouris, P., Chen, Z. & Perebeinos, V. Carbon-based electronics. Nat. Nanotechnol. 2, 605–615 (2007).
Avouris, P., Freitag, M. & Perebeinos, V. Carbon-nanotube photonics and optoelectronics. Nat. Photonics 2, 341–350 (2008).
Sgobba, V. & Guldi, D. M. Carbon nanotubes-electronic/electrochemical properties and application for nanoelectronics and photonics. Chem. Soc. Rev. 38, 165–184 (2009).
Zhang, M. et al. Strong, transparent, multifunctional, carbon nanotube sheets. Science 309, 1215–1219 (2005).
Wu, Z. et al. Transparent, conductive carbon nanotube films. Science 305, 1273–1276 (2004).
Heller, D. A., Baik, S., Eurell, T. E. & Strano, M. S. Single-walled carbon nanotube spectroscopy in live cells: towards long-term labels and optical sensors. Adv. Mater. 17, 2793–2799 (2005).
Tu, X., Hight Walker, A. R., Khripin, C. Y. & Zheng, M. Evolution of DNA sequences toward recognition of metallic armchair carbon nanotubes. J. Am. Chem. Soc. 133, 12998–13001 (2011).
Arnold, M. S., Green, A. A., Hulvat, J. F., Stupp, S. I. & Hersam, M. C. Sorting carbon nanotubes by electronic structure using density differentiation. Nat. Nanotechnol. 1, 60–65 (2006).
Ghosh, S., Bachilo, S. M. & Weisman, R. B. Advanced sorting of single-walled carbon nanotubes by nonlinear density-gradient ultracentrifugation. Nat. Nanotechnol. 5, 443–450 (2010).
Liu, H., Nishide, D., Tanaka, T. & Kataura, H. Large-scale single-chirality separation of single-wall carbon nanotubes by simple gel chromatography. Nat. Commun. 2, 309 (2011).
Dresselhaus, M. S., Dresselhaus, G. & Saito, R. Physics of carbon nanotubes. Carbon 33, 883–891 (1995).
Dai, H. Carbon nanotubes: synthesis, integration, and properties. Acc. Chem. Res. 35, 1035–1044 (2002).
Coleman, J. N., Khan, U., Blau, W. J. & Gun'ko, Y. K. Small but strong: a review of the mechanical properties of carbon nanotube-polymer composites. Carbon 44, 1624–1652 (2006).
Carlson, L. J. & Krauss, T. D. Photophysics of individual single-walled carbon nanotubes. Acc. Chem. Res. 41, 235–243 (2008).
Omachi, H., Segawa, Y. & Itami, K. Synthesis of cycloparaphenylenes and related carbon nanorings: a step toward the controlled synthesis of carbon nanotubes. Acc. Chem. Res. 45, 1378–1389 (2012).
Jasti, R. & Bertozzi, C. R. Progress and challenges for the bottom-up synthesis of carbon nanotubes with discrete chirality. Chem. Phys. Lett. 494, 1–7 (2010).
Yamago, S., Kayahara, E. & Iwamoto, T. Organoplatinum-mediated synthesis of cyclic π-conjugated molecules: towards a new era of three-dimensional aromatic compounds. Chem. Rec. 14, 84–100 (2014).
Lewis, S. E. Cycloparaphenylenes and related nanohoops. Chem. Soc. Rev. 44, 2221–2304 (2015).
Bunz, U. H. F., Menning, S. & Martín, N. para-Connected cyclophenylenes and hemispherical polyarenes: building blocks for single-walled carbon nanotubes? Angew. Chem. Int. Ed. Engl. 51, 7094–7101 (2012).
Baldridge, K. K. & Siegel, J. S. Corannulene-based fullerene fragments C20H10-C50H10: when does a buckybowl become a buckytube? Theor. Chem. Acc. 97, 67–71 (1997).
Parekh, V. C. & Guha, P. C. Synthesis of pp'-diphenylenedimonosulphide. J. Indian Chem. Soc. 11, 95–100 (1934).
Jasti, R., Bhattacharjee, J., Neaton, J. B. & Bertozzi, C. R. Synthesis, characterization, and theory of -, -, and cycloparaphenylene: carbon nanohoop structures. J. Am. Chem. Soc. 130, 17646–17647 (2008).
Takaba, H., Omachi, H., Yamamoto, Y., Bouffard, J. & Itami, K. Selective synthesis of cycloparaphenylene. Angew. Chem. Int. Ed. Engl. 48, 6112–6116 (2009).
Yamago, S., Watanabe, Y. & Iwamoto, T. Synthesis of cycloparaphenylene from a square-shaped tetranuclear platinum complex. Angew. Chem. Int. Ed. Engl. 49, 757–759 (2010).
Fuhrmann, G., Debaerdemaeker, T. & Bauerle, P. C-C bond formation through oxidatively induced elimination of platinum complexes - a novel approach towards conjugated macrocycles. Chem. Commun. 948–949 (2003).
Omachi, H., Segawa, Y. & Itami, K. Synthesis and racemization process of chiral carbon nanorings: a step toward the chemical synthesis of chiral carbon nanotubes. Org. Lett. 13, 2480–2483 (2011).
Hitosugi, S., Nakanishi, W., Yamasaki, T. & Isobe, H. Bottom-up synthesis of finite models of helical (n,m)-single-wall carbon nanotubes. Nat. Commun. 2, 492 (2011).
Matsuno, T., Kamata, S., Hitosugi, S. & Isobe, H. Bottom-up synthesis and structures of π-lengthened tubular macrocycles. Chem. Sci. 4, 3179–3183 (2013).
Kohnke, F. H., Slawin, A. M. Z., Stoddart, J. F. & Williams, D. J. Molecular belts and collars in the making: a hexaepoxyoctacosahydrocyclacene derivative. Angew. Chem. Int. Ed. Engl. 26, 892–894 (1987).
Cory, R. M., McPhail, C. L., Dikmans, A. J. & Vittal, J. J. Macrocyclic cyclophane belts via double Diels–Alder cycloadditions: macroannulation of bisdienes by bisdienophiles. Synthesis of a key precursor to an cyclacene. Tetrahedron Lett. 37, 1983–1986 (1996).
Hitosugi, S., Yamasaki, T. & Isobe, H. Bottom-up synthesis and thread-in-bead structures of finite (n,0)-zigzag single-wall carbon nanotubes. J. Am. Chem. Soc. 134, 12442–12445 (2012).
Scott, L. T. et al. A short, rigid, structurally pure carbon nanotube by stepwise chemical synthesis. J. Am. Chem. Soc. 134, 107–110 (2012).
Petrukhina, M. A. & Scott, L. T. (eds) Fragments of Fullerenes and Carbon Nanotube: Designed Synthesis, Unusual Reactions, and Coordination Chemistry (Wiley, 2012).
Vögtle, F. Concluding remarks. Top. Curr. Chem. 115, 157 (1983).
Iyoda, M., Kuwatani, Y., Nishinaga, T., Takase, M. & Nishiuchi, T. in Fragments of Fullerenes and Carbon Nanotube: Designed Synthesis, Unusual Reactions, and Coordination Chemistry (eds Petrukhina, M. A. & Scott, L. T. ) Ch. 12 (Wiley, 2012).
Nakamura, E., Tahara, K., Matsuo, Y. & Sawamura, M. Synthesis, structure, and aromaticity of a hoop-shaped cyclic benzenoid cyclophenacene. J. Am. Chem. Soc. 125, 2834–2835 (2003).
Yagi, A., Segawa, Y. & Itami, K. Synthesis and properties of cyclo-1,4-naphthylene: a π-extended carbon nanoring. J. Am. Chem. Soc. 134, 2962–2965 (2012).
Ishii, Y., Matsuura, S., Segawa, Y. & Itami, K. Synthesis and dimerization of chlorocycloparaphenylene: a directly connected cycloparaphenylene dimer. Org. Lett. 16, 2174–2176 (2014).
Nishiuchi, T., Feng, X., Enkelmann, V., Wagner, M. & Müllen, K. Three-dimensionally arranged cyclic p-hexaphenylbenzene: toward a bottom-up synthesis of size-defined carbon nanotubes. Chem. Eur. J. 18, 16621–16625 (2012).
Golling, F. E., Quernheim, M., Wagner, M., Nishiuchi, T. & Müllen, K. Concise synthesis of 3D π-extended polyphenylene cylinders. Angew. Chem. Int. Ed. Engl. 53, 1525–1528 (2014).
Quernheim, M. et al. The precise synthesis of phenylene-extended cyclic hexa-peri-hexabenzocoronenes from polyarylated [n]cycloparaphenylenes by the Scholl reaction. Angew. Chem. Int. Ed. Engl. 54, 10341–10346 (2015).
Yu, X. et al. Cap formation engineering: from opened C60 to single-walled carbon nanotubes. Nano Lett. 10, 3343–3349 (2010).
Liu, B. et al. Nearly exclusive growth of small diameter semiconducting single-wall carbon nanotubes from organic chemistry synthetic end-cap molecules. Nano Lett. 15, 586–595 (2015).
Omachi, H., Nakayama, T., Takahashi, E., Segawa, Y. & Itami, K. Initiation of carbon nanotube growth by well-defined carbon nanorings. Nat. Chem. 5, 572–576 (2013).
Sanchez-Valencia, J. R. et al. Controlled synthesis of single-chirality carbon nanotubes. Nature 512, 61–64 (2014).
Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater. 6, 183–191 (2007).
Wu, J., Pisula, W. & Müllen, K. Graphenes as potential material for electronics. Chem. Rev. 107, 718–747 (2007).
Geim, A. K. Graphene: status and prospects. Science 324, 1530–1534 (2009).
Allen, M. J., Tung, V. C. & Kaner, R. B. Honeycomb carbon: a review of graphene. Chem. Rev. 110, 132–145 (2010).
Pumera, M. Graphene-based nanomaterials and their electrochemistry. Chem. Soc. Rev. 39, 4146–4157 (2010).
Schwierz, F. Graphene transistors. Nat. Nanotechnol. 5, 487–496 (2010).
Guo, S. & Dong, S. Graphene nanosheet: synthesis, molecular engineering, thin film, hybrids, and energy and analytical applications. Chem. Soc. Rev. 40, 2644–2672 (2011).
Novoselov, K. S. et al. A roadmap for graphene. Nature 490, 192–200 (2012).
Yan, L. et al. Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials. Chem. Soc. Rev. 41, 97–114 (2012).
Ren, W. & Cheng, H. M. The global growth of graphene. Nat. Nanotechnol. 9, 726–730 (2014).
Georgakilas, V., Perman, J. A., Tucek, J. & Zboril, R. Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures. Chem. Rev. 115, 4744–4822 (2015).
Bai, J., Zhong, X., Jiang, S., Huang, Y. & Duan, X. Graphene nanomesh. Nat. Nanotechnol. 5, 190–194 (2010).
Liang, X. et al. Formation of bandgap and subbands in graphene nanomeshes with sub-10 nm ribbon width fabricated via nanoimprint lithography. Nano Lett. 10, 2454–2460 (2010).
Safron, N. S., Brewer, A. S. & Arnold, M. S. Semiconducting two-dimensional graphene nanoconstriction arrays. Small 7, 492–498 (2011).
Zhang, Y. et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature 459, 820–823 (2009).
Peng, Z., Yan, Z., Sun, Z. & Tour, J. M. Direct growth of bilayer graphene on SiO2 substrates by carbon diffusion through nickel. ACS Nano 5, 8241–8247 (2011).
Elias, D. C. et al. Control of graphene's properties by reversible hydrogenation: evidence for graphane. Science 323, 610–613 (2009).
Cheng, S. H. et al. Reversible fluorination of graphene: evidence of a two-dimensional wide bandgap semiconductor. Phys. Rev. B 81, 205435 (2010).
Watson, M. D., Fechtenkötter, A. & Müllen, K. Big is beautiful – “Aromaticity” revisited from the viewpoint of macromolecular and supramolecular benzene chemistry. Chem. Rev. 101, 1267–1300 (2001).
Feng, X., Pisula, W. & Müllen, K. Large polycyclic aromatic hydrocarbons: synthesis and discotic organization. Pure Appl. Chem. 81, 2203–2224 (2009).
Rieger, R. & Müllen, K. Forever young: polycyclic aromatic hydrocarbons as model cases for structural and optical studies. J. Phys. Org. Chem. 23, 315–325 (2010).
Chen, L., Hernandez, Y., Feng, X. & Müllen, K. From nanographene and graphene nanoribbons to graphene sheets: chemical synthesis. Angew. Chem. Int. Ed. Engl. 51, 7640–7654 (2012).
Itami, K. Toward controlled synthesis of carbon nanotubes and graphenes. Pure Appl. Chem. 84, 907–916 (2012).
Sun, Z., Ye, Q., Chi, C. & Wu, J. Low band gap polycyclic hydrocarbons: from closed-shell near infrared dyes and semiconductors to open-shell radicals. Chem. Soc. Rev. 41, 7857–7889 (2012).
Müllen, K. Graphene as a target for polymer synthesis. Adv. Polym. Sci. 262, 61–92 (2013).
Wu, D., Ge, H. J., Liu, S. H. & Yin, J. Arynes in the synthesis of polycyclic aromatic hydrocarbons. RSC Adv. 3, 22727–22738 (2013).
Müllen, K. Evolution of graphene molecules: structural and functional complexity as driving forces behind nanoscience. ACS Nano 8, 6531–6541 (2014).
Ball, M. et al. Contorted polycyclic aromatics. Acc. Chem. Res. 48, 267–276 (2015).
Narita, A., Feng, X. & Müllen, K. Bottom-up synthesis of chemically precise graphene nanoribbons. Chem. Rec. 15, 295–309 (2015).
Narita, A., Wang, X. Y., Feng, X. & Müllen, K. New advances in nanographene chemistry. Chem. Soc. Rev. 44, 6616–6643 (2015).
Yang, X. et al. Two-dimensional graphene nanoribbons. J. Am. Chem. Soc. 130, 4216–4217 (2008).
Narita, A. et al. Synthesis of structurally well-defined and liquid-phase-processable graphene nanoribbons. Nat. Chem. 6, 126–132 (2014).
Wu, J. et al. From branched polyphenylenes to graphite ribbons. Macromolecules 36, 7082–7089 (2003).
Fogel, Y. et al. Graphitic nanoribbons with dibenzo[e,l]pyrene repeat units: synthesis and self-assembly. Macromolecules 42, 6878–6884 (2009).
Dossel, L., Gherghel, L., Feng, X. & Müllen, K. Graphene nanoribbons by chemists: nanometer-sized, soluble, and defect-free. Angew. Chem. Int. Ed. Engl. 50, 2540–2543 (2011).
Schwab, M. G. et al. Structurally defined graphene nanoribbons with high lateral extension. J. Am. Chem. Soc. 134, 18169–18172 (2012).
Kim, K. T., Jung, J. W. & Jo, W. H. Synthesis of graphene nanoribbons with various widths and its application to thin-film transistor. Carbon 63, 202–209 (2013).
Kim, K. T., Lee, J. W. & Jo, W. H. Charge-transport tuning of solution-processable graphene nanoribbons by substitutional nitrogen doping. Macromol. Chem. Phys. 214, 2768–2773 (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).
El Gemayel, M. et al. Graphene nanoribbon blends with P3HT for organic electronics. Nanoscale 6, 6301–6314 (2014).
Narita, A. et al. Bottom-up synthesis of liquid-phase-processable graphene nanoribbons with near-infrared absorption. ACS Nano 8, 11622–11630 (2014).
Vo, T. H. et al. Large-scale solution synthesis of narrow graphene nanoribbons. Nat. Commun. 5, 3189 (2014).
Vo, T. H. et al. Bottom-up solution synthesis of narrow nitrogen-doped graphene nanoribbons. Chem. Commun. 50, 4172–4174 (2014).
Liu, J. et al. Toward cove-edged low band gap graphene nanoribbons. J. Am. Chem. Soc. 137, 6097–6103 (2015).
Schwab, M. G. et al. Bottom-up synthesis of necklace-like graphene nanoribbons. Chem. Asian J. 10, 2134–2138 (2015).
Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010).
Bjork, J., Stafstrom, S. & Hanke, F. Zipping up: cooperativity drives the synthesis of graphene nanoribbons. J. Am. Chem. Soc. 133, 14884–14887 (2011).
Martin-Gago, J. A. Polycyclic aromatics: on-surface molecular engineering. Nat. Chem. 3, 11–12 (2011).
Blankenburg, S. et al. Intraribbon heterojunction formation in ultranarrow graphene nanoribbons. ACS Nano 6, 2020–2025 (2012).
Huang, H. et al. Spatially resolved electronic structures of atomically precise armchair graphene nanoribbons. Sci. Rep. 2, 983 (2012).
Koch, M., Ample, F., Joachim, C. & Grill, L. Voltage-dependent conductance of a single graphene nanoribbon. Nat. Nanotechnol. 7, 713–717 (2012).
Linden, S. et al. Electronic structure of spatially aligned graphene nanoribbons on Au(788). Phys. Rev. Lett. 108, 216801 (2012).
Ruffieux, P. et al. Electronic structure of atomically precise graphene nanoribbons. ACS Nano 6, 6930–6935 (2012).
Bronner, C. et al. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem. Int. Ed. Engl. 52, 4422–4425 (2013).
Chen, Y. C. et al. Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. ACS Nano 7, 6123–6128 (2013).
Talirz, L. et al. Termini of bottom-up fabricated graphene nanoribbons. J. Am. Chem. Soc. 135, 2060–2063 (2013).
van der Lit, J. et al. Suppression of electron-vibron coupling in graphene nanoribbons contacted via a single atom. Nat. Commun. 4, 2023 (2013).
Abdurakhmanova, N. et al. Synthesis of wide atomically precise graphene nanoribbons from para-oligophenylene based molecular precursor. Carbon 77, 1187–1190 (2014).
Cai, J. et al. Graphene nanoribbon heterojunctions. Nat. Nanotechnol. 9, 896–900 (2014).
Denk, R. et al. Exciton-dominated optical response of ultra-narrow graphene nanoribbons. Nat. Commun. 5, 4253 (2014).
Han, P. et al. Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity. ACS Nano 8, 9181–9187 (2014).
Palma, C. A. et al. Photoinduced C-C reactions on insulators toward photolithography of graphene nanoarchitectures. J. Am. Chem. Soc. 136, 4651–4658 (2014).
Sakaguchi, H. et al. Width-controlled sub-nanometer graphene nanoribbon films synthesized by radical-polymerized chemical vapor deposition. Adv. Mater. 26, 4134–4138 (2014).
Basagni, A. et al. Molecules-oligomers-nanowires-graphene nanoribbons: a bottom-up stepwise on-surface covalent synthesis preserving long-range order. J. Am. Chem. Soc. 137, 1802–1808 (2015).
Chen, Y. C. et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nat. Nanotechnol. 10, 156–160 (2015).
Cloke, R. R. et al. Site-specific substitutional boron doping of semiconducting armchair graphene nanoribbons. J. Am. Chem. Soc. 137, 8872–8875 (2015).
Dienel, T. et al. Resolving atomic connectivity in graphene nanostructure junctions. Nano Lett. 15, 5185–5190 (2015).
Söde, H. et al. Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy. Phys. Rev. B 91, 045429 (2015).
Zhang, H. et al. On-surface synthesis of rylene-type graphene nanoribbons. J. Am. Chem. Soc. 137, 4022–4025 (2015).
Kawai, S. et al. Atomically controlled substitutional boron-doping of graphene nanoribbons. Nat. Commun. 6, 8098 (2015).
Talyzin, A. V. et al. Synthesis of graphene nanoribbons encapsulated in single-walled carbon nanotubes. Nano Lett. 11, 4352–4356 (2011).
Chuvilin, A. et al. Self-assembly of a sulphur-terminated graphene nanoribbon within a single-walled carbon nanotube. Nat. Mater. 10, 687–692 (2011).
Bandow, S., Takizawa, M., Hirahara, K., Yudasaka, M. & Iijima, S. Raman scattering study of double-wall carbon nanotubes derived from the chains of fullerenes in single-wall carbon nanotubes. Chem. Phys. Lett. 337, 48–54 (2001).
Chamberlain, T. W. et al. Size, structure, and helical twist of graphene nanoribbons controlled by confinement in carbon nanotubes. ACS Nano 6, 3943–3953 (2012).
Fujihara, M. et al. Dimerization-initiated preferential formation of coronene-based graphene nanoribbons in carbon nanotubes. J. Phys. Chem. C 116, 15141–15145 (2012).
Lim, H. E. et al. Growth of carbon nanotubes via twisted graphene nanoribbons. Nat. Commun. 4, 2548 (2013).
Lim, H. E. et al. Fabrication and optical probing of highly extended, ultrathin graphene nanoribbons in carbon nanotubes. ACS Nano 9, 5034–5040 (2015).
Fort, E. H., Donovan, P. M. & Scott, L. T. Diels–Alder reactivity of polycyclic aromatic hydrocarbon bay regions: implications for metal-free growth of single-chirality carbon nanotubes. J. Am. Chem. Soc. 131, 16006–16007 (2009).
Fort, E. H. & Scott, L. T. One-step conversion of aromatic hydrocarbon bay regions into unsubstituted benzene rings: a reagent for the low-temperature, metal-free growth of single-chirality carbon nanotubes. Angew. Chem. Int. Ed. Engl. 49, 6626–6628 (2010).
Fort, E. H. & Scott, L. T. Gas-phase Diels–Alder cycloaddition of benzyne to an aromatic hydrocarbon bay region: groundwork for the selective solvent-free growth of armchair carbon nanotubes. Tetrahedron Lett. 52, 2051–2053 (2011).
Li, J., Jiao, C., Huang, K. W. & Wu, J. Lateral extension of π-conjugation along the bay regions of bisanthene through a Diels–Alder cycloaddition reaction. Chem. Eur. J. 17, 14672–14680 (2011).
Fort, E. H., Jeffreys, M. S. & Scott, L. T. Diels–Alder cycloaddition of acetylene gas to a polycyclic aromatic hydrocarbon bay region. Chem. Commun. 48, 8102–8104 (2012).
Konishi, A., Hirao, Y., Matsumoto, K., Kurata, H. & Kubo, T. Facile synthesis and lateral π-expansion of bisanthenes. Chem. Lett. 42, 592–594 (2013).
Schuler, B. et al. From perylene to a 22-ring aromatic hydrocarbon in one-pot. Angew. Chem. Int. Ed. Engl. 53, 9004–9006 (2014).
Ozaki, K., Kawasumi, K., Shibata, M., Ito, H. & Itami, K. One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization. Nat. Commun. 6, 6251 (2015).
Mackay, A. L. & Terrones, H. Diamond from graphite. Nature 352, 762 (1991).
Schwarz, H. A. Gesammelte Mathematische Abhandlungen Vols 1,2 (Springer, 1890).
Lenosky, T., Gonze, X., Teter, M. & Elser, V. Energetics of negatively curved graphitic carbon. Nature 335, 333–335 (1992).
Tagami, M., Liang, Y., Naito, H., Kawazoe, Y. & Kotani, M. Negatively curved cubic carbon crystals with octahedral symmetry. Carbon 76, 266–274 (2014).
Ōsawa, E., Yoshida, M. & Fujita, M. Shape and fantasy of fullerenes. MRS Bull. 19, 33–38 (1994).
Christoph, H. et al. MP2 and DFT calculations on circulenes and an attempt to prepare the second lowest benzolog, circulene. Chem. Eur. J. 14, 5604–5616 (2008).
Kaur, N., Dharamvir, K. & Jindal, V. K. Dimerization and fusion of two C60 molecules. Chem. Phys. 344, 176–184 (2008).
Takashima, A., Nishii, T. & Onoe, J. Formation process and electron-beam incident energy dependence of one-dimensional uneven peanut-shaped C60 polymer studied using in situ high-resolution infrared spectroscopy and density-functional calculations. J. Phys. D: Appl. Phys. 45, 485302 (2012).
Weldon, D. N., Blau, W. J. & Zandbergen, H. W. A high resolution electron microscopy investigation of curvature in carbon nanotubes. Chem. Phys. Lett. 241, 365–372 (1995).
Wei, D. & Liu, Y. The intramolecular junctions of carbon nanotubes. Adv. Mater. 20, 2815–2841 (2008).
lijima, S., Ichihashi, T. & Ando, Y. Pentagons, heptagons and negative curvature in graphite microtubule growth. Nature 356, 776–778 (1992).
Galli, C. & Mandolini, L. The role of ring strain on the ease of ring closure of bifunctional chain molecules. Eur. J. Org. Chem. 2000, 3117–3125 (2000).
Yamamoto, K. et al. Synthesis and characterization of circulene. J. Am. Chem. Soc. 105, 7171–7172 (1983).
Yamamoto, K., Saitho, Y., Iwaki, D. & Ooka, T. [7.7]Circulene, a molecule shaped like a figure of eight. Angew. Chem. Int. Ed. Engl. 30, 1173–1174 (1991).
Yamamoto, K. Extended systems of closed helicene. Synthesis and characterization of  and [7.7]circulene. Pure Appl. Chem. 65, 157–163 (1993).
Rajca, A., Safronov, A., Rajca, S. & Shoemaker, R. Double helical octaphenylene. Angew. Chem. Int. Ed. Engl. 36, 488–491 (1997).
Feng, C.-N., Kuo, M.-Y. & Wu, Y.-T. Synthesis, structural analysis, and properties of circulenes. Angew. Chem. Int. Ed. Engl. 52, 7791–7794 (2013).
Sakamoto, Y. & Suzuki, T. Tetrabenzocirculene: aromatic saddles from negatively curved graphene. J. Am. Chem. Soc. 135, 14074–14077 (2013).
Miller, R. W., Duncan, A. K., Schneebeli, S. T., Gray, D. L. & Whalley, A. C. Synthesis and structural data of tetrabenzocirculene. Chem. Eur. J. 20, 3705–3711 (2014).
Cheung, K. Y., Xu, X. & Miao, Q. Aromatic saddles containing two heptagons. J. Am. Chem. Soc. 137, 3910–3914 (2015).
Kawasumi, K., Zhang, Q., Segawa, Y., Scott, L. T. & Itami, K. A grossly warped nanographene and the consequences of multiple odd-membered-ring defects. Nat. Chem. 5, 739–744 (2013).
Grzybowski, M., Skonieczny, K., Butenschö n, H. & Gryko, D. T. Comparison of oxidative aromatic coupling and the Scholl reaction. Angew. Chem. Int. Ed. Engl. 52, 9900–9930 (2013).
Mochida, K., Kawasumi, K., Segawa, Y. & Itami, K. Direct arylation of polycyclic aromatic hydrocarbons through palladium catalysis. J. Am. Chem. Soc. 133, 10716–10719 (2011).
Eliseeva, M. N. & Scott, L. T. Pushing the Ir-catalyzed C–H polyborylation of aromatic compounds to maximum capacity by exploiting reversibility. J. Am. Chem. Soc. 134, 15169–15172 (2012).
This work was supported by the Exploratory Research for Advanced Technology (ERATO) program from the Japan Science and Technology Agency (JST) (K.I.). The authors thank A. Miyazaki for critical comments and H. Hirukawa for graphics.
The authors declare no competing interests.
About this article
Cite this article
Segawa, Y., Ito, H. & Itami, K. Structurally uniform and atomically precise carbon nanostructures. Nat Rev Mater 1, 15002 (2016). https://doi.org/10.1038/natrevmats.2015.2
Nature Synthesis (2022)
Rapid access to polycyclic N-heteroarenes from unactivated, simple azines via a base-promoted Minisci-type annulation
Nature Communications (2022)
Science China Chemistry (2022)
Photosynthesis Research (2022)
Nature Chemistry (2021)