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Nano Research 2021, 14(12): 4754-4759 https://doi.org/10.1007/s12274-021-3419-2
Research Article | Open Access | Issue | Published: 23 April 2021

On-surface activation of benzylic C–H bonds for the synthesis of pentagon-fused graphene nanoribbons

Show Author's Information Xiushang Xu1,3,§,  Marco Di Giovannantonio2,†,§,  José I. Urgel2,‡,  Carlo A. Pignedoli2,  Pascal Ruffieux2,  Klaus Müllen1,4( ),  Roman Fasel2( ),  Akimitsu Narita1,3( )
Max Planck Institute for Polymer Research 55128 Mainz Germany
Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory 8600 Dübendorf Switzerland
Organic and Carbon Nanomaterials Unit Okinawa Institute of Science and Technology Graduate University 1919-1 Tancha, Onna-son, Kunigami-gun, Okinawa 904-0495 Japan
Institute of Physical Chemistry Johannes Gutenberg University Mainz Duesbergweg 10-14, 55128 Mainz Germany

§ Xiushang Xu and Marco Di Giovannantonio contributed equally to this work.

† Present address: Istituto di Struttura della Materia-CNR (ISM-CNR), via Fosso del Cavaliere 100, 00133 Roma, Italy

Keywords:
graphene nanoribbons, on-surface synthesis, scanning-tunneling microscope, noncontact atomic force microscope, C–H activation
Topics:
Graphene nanoribbon
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Xu X, Giovannantonio MD, Urgel JI, et al. On-surface activation of benzylic C–H bonds for the synthesis of pentagon-fused graphene nanoribbons. Nano Research, 2021, 14(12): 4754-4759. https://doi.org/10.1007/s12274-021-3419-2
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Abstract Full text Electronic supplementary material About this article

Graphene nanoribbons (GNRs) have potential for applications in electronic devices. A key issue, thereby, is the fine-tuning of their electronic characteristics, which can be achieved through subtle structural modifications. These are not limited to the conventional armchair, zigzag, and cove edges, but also possible through incorporation of non-hexagonal rings. On-surface synthesis enables the fabrication and visualization of GNRs with atomically precise chemical structures, but strategies for the incorporation of non-hexagonal rings have been underexplored. Herein, we describe the on-surface synthesis of armchair-edged GNRs with incorporated five-membered rings through the C-H activation and cyclization of benzylic methyl groups. Ortho-Tolyl-substituted dibromobianthryl was employed as the precursor monomer, and visualization of the resulting structures after annealing at 300 ℃ on a gold surface by high-resolution noncontact atomic force microscopy clearly revealed the formation of methylene-bridged pentagons at the GNR edges. These persisted after annealing at 340 ℃, along with a few fully conjugated pentagons having singly-hydrogenated apexes. The benzylic methyl groups could also migrate or cleave-off, resulting in defects lacking the five- membered rings. Moreover, unexpected and unique structural rearrangements, including the formation of embedded heptagons, were observed. Despite the coexistence of different reaction pathways that hamper selective synthesis of a uniform structure, our results provide novel insights into on-surface reactions en route to functional, non-benzenoid carbon nanomaterials.


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Electronic supplementary material
About this article

On-surface activation of benzylic C–H bonds for the synthesis of pentagon-fused graphene nanoribbons

Show Author's information Xiushang Xu1,3,§, Marco Di Giovannantonio2,†,§, José I. Urgel2,‡, Carlo A. Pignedoli2, Pascal Ruffieux2, Klaus Müllen1,4( ), Roman Fasel2( ), Akimitsu Narita1,3( )
Max Planck Institute for Polymer Research 55128 Mainz Germany
Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory 8600 Dübendorf Switzerland
Organic and Carbon Nanomaterials Unit Okinawa Institute of Science and Technology Graduate University 1919-1 Tancha, Onna-son, Kunigami-gun, Okinawa 904-0495 Japan
Institute of Physical Chemistry Johannes Gutenberg University Mainz Duesbergweg 10-14, 55128 Mainz Germany

§ Xiushang Xu and Marco Di Giovannantonio contributed equally to this work.

† Present address: Istituto di Struttura della Materia-CNR (ISM-CNR), via Fosso del Cavaliere 100, 00133 Roma, Italy

Abstract

Graphene nanoribbons (GNRs) have potential for applications in electronic devices. A key issue, thereby, is the fine-tuning of their electronic characteristics, which can be achieved through subtle structural modifications. These are not limited to the conventional armchair, zigzag, and cove edges, but also possible through incorporation of non-hexagonal rings. On-surface synthesis enables the fabrication and visualization of GNRs with atomically precise chemical structures, but strategies for the incorporation of non-hexagonal rings have been underexplored. Herein, we describe the on-surface synthesis of armchair-edged GNRs with incorporated five-membered rings through the C-H activation and cyclization of benzylic methyl groups. Ortho-Tolyl-substituted dibromobianthryl was employed as the precursor monomer, and visualization of the resulting structures after annealing at 300 ℃ on a gold surface by high-resolution noncontact atomic force microscopy clearly revealed the formation of methylene-bridged pentagons at the GNR edges. These persisted after annealing at 340 ℃, along with a few fully conjugated pentagons having singly-hydrogenated apexes. The benzylic methyl groups could also migrate or cleave-off, resulting in defects lacking the five- membered rings. Moreover, unexpected and unique structural rearrangements, including the formation of embedded heptagons, were observed. Despite the coexistence of different reaction pathways that hamper selective synthesis of a uniform structure, our results provide novel insights into on-surface reactions en route to functional, non-benzenoid carbon nanomaterials.

Keywords: graphene nanoribbons, on-surface synthesis, scanning-tunneling microscope, noncontact atomic force microscope, C–H activation

References(50)

1

Yano, Y.; Mitoma, N.; Ito, H.; Itami, K. A quest for structurally uniform graphene nanoribbons: Synthesis, properties, and applications. J. Org. Chem. 2020, 85, 4–33.
DOI Google Scholar
2

Narita, A.; Wang, X. Y.; Feng, X. L.; Müllen, K. New advances in nanographene chemistry. Chem. Soc. Rev. 2015, 44, 6616–6643.
DOI Google Scholar
3

Xu, X. S.; Müllen, K.; Narita, A. Syntheses and characterizations of functional polycyclic aromatic hydrocarbons and graphene nanoribbons. Bull. Chem. Soc. Jpn. 2020, 93, 490–506.
DOI Google Scholar
4

Chen, Z. P.; Narita, A.; Müllen, K. Graphene nanoribbons: On-surface synthesis and integration into electronic devices. Adv. Mater. 2020, 32, 2001893.
DOI Google Scholar
5

Clair, S.; de Oteyza, D. G. Controlling a chemical coupling reaction on a surface: Tools and strategies for on-surface synthesis. Chem. Rev. 2019, 119, 4717–4776.
DOI Google Scholar
6

Dong, L.; Liu, P. N.; Lin, N. Surface-activated coupling reactions confined on a surface. Acc. Chem. Res. 2015, 48, 2765–2774.
DOI Google Scholar
7

Niu, T. C.; Zhang, J. L.; Chen, W. Atomic mechanism for the growth of wafer-scale single-crystal graphene: Theoretical perspective and scanning tunneling microscopy investigations. 2D Mater. 2017, 4, 042002.
DOI Google Scholar
8

Shen, Q.; Gao, H. Y.; Fuchs, H. Frontiers of on-surface synthesis: From principles to applications. Nano Today 2017, 13, 77–96.
DOI Google Scholar
9

Gross, L.; Schuler, B.; Pavliček, N.; Fatayer, S.; Majzik, Z.; Moll, N.; Peña, D.; Meyer, G. Atomic force microscopy for molecular structure elucidation. Angew. Chem., Int. Ed. 2018, 57, 3888–3908.
DOI Google Scholar
10

Zhou, X. H.; Yu, G. Modified engineering of graphene nanoribbons prepared via on-surface synthesis. Adv. Mater. 2020, 32, 1905957.
DOI Google Scholar
11

Cai, J. M.; Ruffieux, P.; Jaafar, R.; Bieri, M.; Braun, T.; Blankenburg, S.; Muoth, M.; Seitsonen, A. P.; Saleh, M.; Feng, X. L. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 2010, 466, 470–473.
DOI Google Scholar
12

Zhang, H. M.; Lin, H. P.; Sun, K. W.; Chen, L.; Zagranyarski, Y.; Aghdassi, N.; Duhm, S.; Li, Q.; Zhong, D. Y.; Li, Y. Y. et al. On- surface synthesis of rylene-type graphene nanoribbons. J. Am. Chem. Soc. 2015, 137, 4022–4025.
DOI Google Scholar
13

Denk, R.; Hohage, M.; Zeppenfeld, P.; Cai, J. M.; Pignedoli, C. A.; Söde, H.; Fasel, R.; Feng, X. L.; Müllen, K.; Wang, S. D. et al. Exciton- dominated optical response of ultra-narrow graphene nanoribbons. Nat. Commun. 2014, 5, 4253.
DOI Google Scholar
14

Basagni, A.; Sedona, F.; Pignedoli, C. A.; Cattelan, M.; Nicolas, L.; Casarin, M.; Sambi, M. Molecules–oligomers–nanowires–graphene nanoribbons: A bottom-up stepwise on-surface covalent synthesis preserving long-range order. J. Am. Chem. Soc. 2015, 137, 1802–1808.
DOI Google Scholar
15

Talirz, L.; Söde, H.; Dumslaff, T.; Wang, S. Y.; Sanchez-Valencia, J. R.; Liu, J.; Shinde, P.; Pignedoli, C. A.; Liang, L. B.; Meunier, V. et al. On-surface synthesis and characterization of 9-atom wide armchair graphene nanoribbons. ACS Nano 2017, 11, 1380–1388.
DOI Google Scholar
16

Chen, Y. C.; de Oteyza, D. G.; Pedramrazi, Z.; Chen, C.; Fischer, F. R.; Crommie, M. F. Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. ACS Nano 2013, 7, 6123–6128.
DOI Google Scholar
17

Abdurakhmanova, N.; Amsharov, N.; Stepanow, S.; Jansen, M.; Kern, K.; Amsharov, K. Synthesis of wide atomically precise graphene nanoribbons from para-oligophenylene based molecular precursor. Carbon 2014, 77, 1187–1190.
DOI Google Scholar
18

Sun, K. W.; Ji, P. H.; Zhang, J. J.; Wang, J. X.; Li, X. C.; Xu, X.; Zhang, H. M.; Chi, L. F. On-surface synthesis of 8-and 10-armchair graphene nanoribbons. Small 2019, 15, 1804526.
DOI Google Scholar
19

Yamaguchi, J.; Hayashi, H.; Jippo, H.; Shiotari, A.; Ohtomo, M.; Sakakura, M.; Hieda, N.; Aratani, N.; Ohfuchi, M.; Sugimoto, Y. et al. Small bandgap in atomically precise 17-atom-wide armchair-edged graphene nanoribbons. Comms. Mater. 2020, 1, 36.
DOI Google Scholar
20

Ruffieux, P.; Wang, S. Y.; Yang, B.; Sánchez-Sánchez, C.; Liu, J.; Dienel, T.; Talirz, L.; Shinde, P.; Pignedoli, C. A.; Passerone, D. et al. On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature 2016, 531, 489–492.
DOI Google Scholar
21

Costa, P. S.; Teeter, J. D.; Enders, A.; Sinitskii, A. Chevron-based graphene nanoribbon heterojunctions: Localized effects of lateral extension and structural defects on electronic properties. Carbon 2018, 134, 310–315.
DOI Google Scholar
22

Han, P.; Akagi, K.; Federici Canova, F.; Mutoh, H.; Shiraki, S.; Iwaya, K.; Weiss, P. S.; Asao, N.; Hitosugi, T. Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity. ACS Nano 2014, 8, 9181–9187.
DOI Google Scholar
23

Miao, D. D.; Daigle, M.; Lucotti, A.; Boismenu-Lavoie, J.; Tommasini, M.; Morin, J. F. Toward thiophene-annulated graphene nanoribbons. Angew. Chem., Int. Ed. 2018, 57, 3588–3592.
DOI Google Scholar
24

Wang, X. Y.; Urgel, J. I.; Barin, G. B.; Eimre, K.; Di Giovannantonio, M.; Milani, A.; Tommasini, M.; Pignedoli, C. A.; Ruffieux, P.; Feng, X. L. et al. Bottom-up synthesis of heteroatom-doped chiral graphene nanoribbons. J. Am. Chem. Soc. 2018, 140, 9104–9107.
DOI Google Scholar
25

Kawai, S.; Saito, S.; Osumi, S.; Yamaguchi, S.; Foster, A. S.; Spijker, P.; Meyer, E. Atomically controlled substitutional boron-doping of graphene nanoribbons. Nat. Commun. 2015, 6, 8098.
DOI Google Scholar
26

Cloke, R. R.; Marangoni, T.; Nguyen, G. D.; Joshi, T.; Rizzo, D. J.; Bronner, C.; Cao, T.; Louie, S. G.; Crommie, M. F.; Fischer, F. R. Site-specific substitutional boron doping of semiconducting armchair graphene nanoribbons. J. Am. Chem. Soc. 2015, 137, 8872–8875.
DOI Google Scholar
27

Kawai, S.; Nakatsuka, S.; Hatakeyama, T.; Pawlak, R.; Meier, T.; Tracey, J.; Meyer, E.; Foster, A. S. Multiple heteroatom substitution to graphene nanoribbon. Sci. Adv. 2018, 4, eaar7181.
DOI Google Scholar
28

Bronner, C.; Stremlau, S.; Gille, M.; Brauße, F.; Haase, A.; Hecht, S.; Tegeder, P. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem., Int. Ed. 2013, 52, 4422–4425.
DOI Google Scholar
29

Zhang, Y. F.; Zhang, Y.; Li, G.; Lu, J. C.; Que, Y. D.; Chen, H.; Berger, R.; Feng, X. L.; Müllen, K.; Lin, X. et al. Sulfur-doped graphene nanoribbons with a sequence of distinct band gaps. Nano Res. 2017, 10, 3377–3384.
DOI Google Scholar
30

Durr, R. A.; Haberer, D.; Lee, Y. L.; Blackwell, R.; Kalayjian, A. M.; Marangoni, T.; Ihm, J.; Louie, S. G.; Fischer, F. R. Orbitally matched edge-doping in graphene nanoribbons. J. Am. Chem. Soc. 2018, 140, 807–813.
DOI Google Scholar
31

Nguyen, G. D.; Toma, F. M.; Cao, T.; Pedramrazi, Z.; Chen, C.; Rizzo, D. J.; Joshi, T.; Bronner, C.; Chen, Y. C.; Favaro, M. et al. Bottom-up synthesis of N = 13 sulfur-doped graphene nanoribbons. J. Phys. Chem. C 2016, 120, 2684–2687.
DOI Google Scholar
32

Moreno, C.; Paradinas, M.; Vilas-Varela, M.; Panighel, M.; Ceballos, G.; Peña, D.; Mugarza, A. On-surface synthesis of superlattice arrays of ultra-long graphene nanoribbons. Chem. Commun. 2018, 54, 9402–9405.
DOI Google Scholar
33

Moreno, C.; Vilas-Varela, M.; Kretz, B.; Garcia-Lekue, A.; Costache, M. V.; Paradinas, M.; Panighel, M.; Ceballos, G.; Valenzuela, S. O.; Peña, D. et al. Bottom-up synthesis of multifunctional nanoporous graphene. Science 2018, 360, 199–203.
DOI Google Scholar
34

Fan, Q. T.; Martin-Jimenez, D.; Ebeling, D.; Krug, C. K.; Brechmann, L.; Kohlmeyer, C.; Hilt, G.; Hieringer, W.; Schirmeisen, A.; Gottfried, J. M. Nanoribbons with nonalternant topology from fusion of polyazulene: Carbon allotropes beyond graphene. J. Am. Chem. Soc. 2019, 141, 17713–17720.
DOI Google Scholar
35

Di Giovannantonio, M.; Urgel, J. I.; Beser, U.; Yakutovich, A. V.; Wilhelm, J.; Pignedoli, C. A.; Ruffieux, P.; Narita, A.; Müllen, K.; Fasel, R. On-surface synthesis of indenofluorene polymers by oxidative five-membered ring formation. J. Am. Chem. Soc. 2018, 140, 3532–3536.
DOI Google Scholar
36

Di Giovannantonio, M.; Eimre, K.; Yakutovich, A. V.; Chen, Q.; Mishra, S.; Urgel, J. I.; Pignedoli, C. A.; Ruffieux, P.; Müllen, K.; Narita, A. et al. On-surface synthesis of antiaromatic and open-shell indeno [2, 1-b] fluorene polymers and their lateral fusion into porous ribbons. J. Am. Chem. Soc. 2019, 141, 12346–12354.
DOI Google Scholar
37

Di Giovannantonio, M.; Chen, Q.; Urgel, J. I.; Ruffieux, P.; Pignedoli, C. A.; Müllen, K.; Narita, A.; Fasel, R. On-surface synthesis of oligo (indenoindene). J. Am. Chem. Soc. 2020, 142, 12925−12929.
DOI Google Scholar
38

Yazaki, R.; Ohshima, T. Recent strategic advances for the activation of benzylic C-H bonds for the formation of C-C bonds. Tetrahedron Lett. 2019, 60, 151225.
DOI Google Scholar
39

Xue, X. S.; Ji, P. J.; Zhou, B. Y.; Cheng, J. P. The essential role of bond energetics in C-H activation/functionalization. Chem. Rev. 2017, 117, 8622–8648.
DOI Google Scholar
40

Gross, L.; Mohn, F.; Moll, N.; Liljeroth, P.; Meyer, G. The chemical structure of a molecule resolved by atomic force microscopy. Science 2009, 325, 1110–1114.
DOI Google Scholar
41

Betancourt, S. S.; Johansen, Y. B.; Forsythe, J. C.; Rinna, J.; Christoffersen, K.; Skillingstad, P.; Achourov, V.; Canas, J.; Chen, L.; Pomerantz, A. E. et al. Gravitational gradient of asphaltene molecules in an oilfield reservoir with light oil. Energy Fuels 2018, 32, 4911– 4924.
DOI Google Scholar
42

Lohr, T. G.; Urgel, J. I.; Eimre, K.; Liu, J. Z.; Di Giovannantonio, M.; Mishra, S.; Berger, R.; Ruffieux, P.; Pignedoli, C. A.; Fasel, R. et al. On-surface synthesis of non-benzenoid nanographenes by oxidative ring-closure and ring-rearrangement reactions. J. Am. Chem. Soc. 2020, 142, 13565–13572.
DOI Google Scholar
43

Gross, L. Recent advances in submolecular resolution with scanning probe microscopy. Nat. Chem. 2011, 3, 273–278.
DOI Google Scholar
44

Giessibl, F. J. Atomic resolution on Si(111)-(7 × 7) by noncontact atomic force microscopy with a force sensor based on a quartz tuning fork. Appl. Phys. Lett. 2000, 76, 1470–1472.
DOI Google Scholar
45

Bartels, L.; Meyer, G.; Rieder, K. H.; Velic, D.; Knoesel, E.; Hotzel, A.; Wolf, M.; Ertl, G. Dynamics of electron-induced manipulation of individual CO molecules on Cu(111). Phys. Rev. Lett. 1998, 80, 2004–2007.
DOI Google Scholar
46

Giannozzi, P.; Andreussi, O.; Brumme, T.; Bunau, O.; Nardelli, M. B.; Calandra, M.; Car, R.; Cavazzoni, C.; Ceresoli, D.; Cococcioni, M. et al. Advanced capabilities for materials modelling with QUANTUM ESPRESSO. J. Phys.: Condens. Matter 2017, 29, 465901.
DOI Google Scholar
47

Prandini, G.; Marrazzo, A.; Castelli, I. E.; Mounet, N.; Marzari, N. Precision and efficiency in solid-state pseudopotential calculations. npj Comput. Mater. 2018, 4, 72.
DOI Google Scholar
48

Yakutovich, A. V.; Eimre, K.; Schütt, O.; Talirz, L.; Adorf, C. S.; Andersen, C. W.; Ditler, E.; Du, D.; Passerone, D.; Smit, B. et al. AiiDAlab – an ecosystem for developing, executing, and sharing scientific workflows. Comput. Mater. Sci. 2021, 188, 110165.
DOI Google Scholar
49

Pizzi, G.; Cepellotti, A.; Sabatini, R.; Marzari, N.; Kozinsky, B. AiiDA: Automated interactive infrastructure and database for computational science. Comput. Mater. Sci. 2016, 111, 218–230.
DOI Google Scholar
50
Xu X. S.; Di Giovannantonio M.; Urgel, J. I.; Pignedoli, C. A.; Ruffieux, P.; Müllen, K.; Fasel, R.; Narita, A. On-surface activation of benzylic C-H bonds for the synthesis of pentagon-fused graphene nanoribbons. Materials Cloud Archive 2021. 63 (2021), doi: 10.24435/materialscloud:xj-bb.https://doi.org/10.1007/s12274-021-3419-2
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Acknowledgements
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Publication history

Received: 15 January 2021
Revised: 21 February 2021
Accepted: 23 February 2021
Published: 23 April 2021
Issue date: December 2021

Copyright

© The Author(s) 2021

Acknowledgements

Acknowledgements

We are grateful for the financial support by the Max Planck Society, the Swiss National Science Foundation under Grant No. 200020_182015, the NCCR MARVEL funded by the Swiss National Science Foundation (No. 51NF40-182892), the European Union's Horizon 2020 research and innovation programme under grant agreement number 785219 (Graphene Flagship Core 2), the Office of Naval Research (No. N00014- 18-1-2708), and the Okinawa Institute of Science and Technology Graduate University (OIST). The Swiss National Supercomputing Centre (CSCS) under project ID s904 is acknowledged for computational resources. Skillful technical assistance by Lukas Rotach is gratefully acknowledged.

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