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Surface-confined alternating copolymerization with molecular precision by stoichiometric control

Author

Listed:
  • Lingbo Xing

    (Peking University)

  • Jie Li

    (Peking University)

  • Yuchen Bai

    (Peking University)

  • Yuxuan Lin

    (Peking University)

  • Lianghong Xiao

    (Peking University)

  • Changlin Li

    (Peking University)

  • Dahui Zhao

    (Peking University)

  • Yongfeng Wang

    (Peking University)

  • Qiwei Chen

    (Peking University)

  • Jing Liu

    (Peking University)

  • Kai Wu

    (Peking University)

Abstract

Keen desires for artificial mimicry of biological polymers and property improvement of synthesized ones have triggered intensive explorations for sequence-controlled copolymerization. However, conventional synthesis faces great challenges to achieve this goal due to the strict requirements on reaction kinetics of comonomer pairs and tedious synthetic processes. Here, sequence-controlled alternating copolymerization with molecular precision is realized on surface. The stoichiometric control serves as a thermodynamic strategy to steer the polymerization selectivity, which enables the selective alternating organometallic copolymerization via intermolecular metalation of 4,4”-dibromo-p-terphenyl (P-Br) and 2,5-diethynyl-1,4-bis(phenylethynyl)benzene (A-H) with Ag adatoms on Ag(111) at P-Br: A-H = 2, as verified by scanning tunneling microscopy and density functional theory studies. In contrast, homopolymerization yield increases as the stoichiometric ratio deviates from 2. The microscopic characterizations rationalize the mechanism, providing a delicate explanation of the stoichiometry-dependent polymerization. These findings pave a way to actualizing an efficient sequence control of copolymerization by surface chemistry.

Suggested Citation

  • Lingbo Xing & Jie Li & Yuchen Bai & Yuxuan Lin & Lianghong Xiao & Changlin Li & Dahui Zhao & Yongfeng Wang & Qiwei Chen & Jing Liu & Kai Wu, 2024. "Surface-confined alternating copolymerization with molecular precision by stoichiometric control," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-44955-3
    DOI: 10.1038/s41467-024-44955-3
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    References listed on IDEAS

    as
    1. Jing Liu & Qiwei Chen & Kang Cai & Jie Li & Yaru Li & Xiao Yang & Yajie Zhang & Yongfeng Wang & Hao Tang & Dahui Zhao & Kai Wu, 2019. "Stepwise on-surface dissymmetric reaction to construct binodal organometallic network," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    2. Jing Liu & Jie Li & Zhen Xu & Xiong Zhou & Qiang Xue & Tianhao Wu & Mingjun Zhong & Ruoning Li & Rong Sun & Ziyong Shen & Hao Tang & Song Gao & Bingwu Wang & Shimin Hou & Yongfeng Wang, 2021. "On-surface preparation of coordinated lanthanide-transition-metal clusters," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    3. Shuaipeng Xing & Zhe Zhang & Xiyu Fei & Wei Zhao & Ran Zhang & Tao Lin & Danli Zhao & Huanxin Ju & Hu Xu & Jian Fan & Junfa Zhu & Yu-qiang Ma & Ziliang Shi, 2019. "Selective on-surface covalent coupling based on metal-organic coordination template," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    4. Jian Zhang & Jinxin Wang & Chang Wei & Yanfang Wang & Guanyu Xie & Yongfang Li & Mao Li, 2020. "Rapidly sequence-controlled electrosynthesis of organometallic polymers," Nature Communications, Nature, vol. 11(1), pages 1-8, December.
    5. Yi-Qi Zhang & Nenad Kepčija & Martin Kleinschrodt & Katharina Diller & Sybille Fischer & Anthoula C. Papageorgiou & Francesco Allegretti & Jonas Björk & Svetlana Klyatskaya & Florian Klappenberger & M, 2012. "Homo-coupling of terminal alkynes on a noble metal surface," Nature Communications, Nature, vol. 3(1), pages 1-8, January.
    6. Tao Wang & Haifeng Lv & Jianmin Huang & Huan Shan & Lin Feng & Yahui Mao & Jinyi Wang & Wenzhao Zhang & Dong Han & Qian Xu & Pingwu Du & Aidi Zhao & Xiaojun Wu & Steven L. Tait & Junfa Zhu, 2019. "Reaction selectivity of homochiral versus heterochiral intermolecular reactions of prochiral terminal alkynes on surfaces," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
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