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Homochiral polymerization-driven selective growth of graphene nanoribbons

Abstract

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.

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Figure 1: Selective growth of GNRs.
Figure 2: STM images of stepwise dehydrogenated chains and the dehydrogenation mechanism.
Figure 3: Mechanism of surface-induced homochiral polymerization in a chain.
Figure 4: FET characteristics of acene-type GNRs.

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Acknowledgements

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.

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S.S. and T.N. conducted the synthesis, T.K. conducted the STM experiments and T.N. performed the theoretical calculations. H.S. supervised all experiments and wrote the main text, and T.N. wrote the Supplementary Information.

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Correspondence to Hiroshi Sakaguchi.

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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

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