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Identifying the convergent reaction path from predesigned assembled structures: Dissymmetrical dehalogenation of Br2Py on Ag(111)

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Abstract

On-surface Ullmann coupling has been intensely utilized for the tailor-made fabrication of conjugated frameworks towards molecular electronics, however, reaction mechanisms are still limitedly understood. Herein, we provide a comprehensive elucidation of the surface Ullmann coupling of 2,7-dibromopyrene (Br2Py) on Ag(111) by scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density function theory (DFT), and reveal that the Ullmann reaction path is unique regardless of predesigned assembled structures. By manipulating deposition conditions, diverse assembled architectures have been constructed for Br2Py on Ag(111), including the ladder phase, parallel arrangement, hexagonal patterns from monomers or Kagome lattices based on organometallic (OM) dimers. Intriguingly, stepwise annealing leads to an identical reaction diagram for the surface Ullmann coupling from individual assembled structures convergent into the brick-wall-pattern OM dimers first, which is deemed to be a stable phase, and then into elongated OM chains in order and eventually long-range polymers with direct C-C coupling. While the reaction mechanism is demonstrated to be dominated by the metal coordinated and halogen bonding motifs, interestingly, it has also been revealed that surface adatoms and dissociated Br atoms play a crucial role in coupling reactions. In contrast to previous reports demonstrating the manipulation of Ullmann reactions by preassembled strategy, herein, weak intermolecular interaction in assembled nanostructures is immediately suppressed by strong covalent bonding during reactions. Importantly, our report proposes essential insights on fundamental understanding of surface Ullmann coupling towards high-yield surface synthesis.

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Acknowledgements

Fruitful discussions with Dr. Qitang Fan are greatly appreciated. This work was financially supported by National Natural Science Foundation of China (Nos. 11874380, 11874427, and U1732267), the National Key Research and Development Program of China (No. 2016YFA040130201) and the Hundred Talents Program of Chinese Academy of Sciences.

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Authors and Affiliations

  1. Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201000, China

    Jinping Hu, Kongchao Shen, Huan Zhang, Chaoqin Huang, Yaobo Huang, Zheng Jiang & Fei Song

  2. University of Chinese Academy of Sciences, Beijing, 100100, China

    Jinping Hu, Huan Zhang, Chaoqin Huang, Yaobo Huang, Zheng Jiang & Fei Song

  3. Shanghai Synchrotron Radiation Faciality, Zhangjiang Laboratory, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201000, China

    Zhaofeng Liang, Lei Xie, Yaobo Huang, Zheng Jiang & Fei Song

  4. Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Suzhou, 215123, China

    Kongchao Shen & Jianxin Tang

  5. School of Physics Science and Electronics, Central South University, Changsha, 410083, China

    Han Huang

  6. State Key Laboratory of Urban Water Resource and Environment, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China

    Miao Yu

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  1. Jinping Hu
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Identifying the convergent reaction path from predesigned assembled structures: Dissymmetrical dehalogenation of Br2Py on Ag(111)

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Hu, J., Liang, Z., Shen, K. et al. Identifying the convergent reaction path from predesigned assembled structures: Dissymmetrical dehalogenation of Br2Py on Ag(111). Nano Res. 14, 4704–4713 (2021). https://doi.org/10.1007/s12274-021-3409-9

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