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Research Article

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

Jinping Hu1,2, Zhaofeng Liang3, Kongchao Shen1,4, Lei Xie3, Huan Zhang1,2, Chaoqin Huang1,2, Yaobo Huang1,2,3, Han Huang5, Jianxin Tang4, Zheng Jiang1,2,3, Miao Yu6, Fei Song1,2,3( )
Key Laboratory of Interfacial Physics and Technology Shanghai Institute of Applied Physics Chinese Academy of Sciences Shanghai 201000 China
University of Chinese Academy of Sciences Beijing 100100 China
Shanghai Synchrotron Radiation Faciality Zhangjiang Laboratory Shanghai Advanced Research InstituteChinese Academy of Sciences Shanghai 201000 China
Institute of Functional Nano & Soft Materials (FUNSOM) Soochow University Suzhou 215123 China
School of Physics Science and Electronics Central South University Changsha 410083 China
State Key Laboratory of Urban Water Resource and Environment School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin 150001 China
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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.

Keywords

self-assemblyUllmann couplingorganometallic intermediatesreaction pathscanning tunneling microscopy

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Nano Research
Volume 14 Issue 12,
December 2021
Pages 4704-4713
DOI: 10.1007/s12274-021-3409-9
Cite this article:
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 Research, 2021, 14(12): 4704-4713. https://doi.org/10.1007/s12274-021-3409-9
Topics:
Self assembled monolayers

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Received: 26 December 2020
Revised: 18 February 2021
Accepted: 21 February 2021
Published: 08 April 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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