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Discrete Linear–Branched Block Copolymer with Broken Architectural Symmetry
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    Discrete Linear–Branched Block Copolymer with Broken Architectural Symmetry
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    • Zhuang Ma
      Zhuang Ma
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
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    • Dongdong Zhou
      Dongdong Zhou
      College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610065, China
    • Miao Xu
      Miao Xu
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
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    • Zhanhui Gan
      Zhanhui Gan
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
      More by Zhanhui Gan
    • Tianyu Zheng
      Tianyu Zheng
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
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    • Shuai Wang
      Shuai Wang
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
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    • Rui Tan*
      Rui Tan
      College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
      *Email [email protected]
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    • Xue-Hui Dong*
      Xue-Hui Dong
      South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
      Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou 510640, China
      *Email [email protected]
      More by Xue-Hui Dong
    Other Access OptionsSupporting Information (1)

    Macromolecules

    Cite this: Macromolecules 2023, 56, 3, 833–840
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    https://doi.org/10.1021/acs.macromol.2c02529
    Published February 6, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    Rationally introducing chain length heterogeneity, such as binary blending, is a robust approach to regulate phase behavior of block copolymers. This work designed a library of discrete linear–branched block copolymers bearing two unequal branches. Diverse ordered nanostructures, including complex Frank–Kasper phases and quasicrystalline phase, were captured by tuning the compositional and architectural asymmetry. The precise chemistry rules out the interferences associated with statistical distribution, while the discrete feature decouples the intertwined variables. Compared with the symmetric counterparts, the synergies between the long and short chains effectively release the packing frustration during the formation of ordered structures, leading to a significant increase of lattice dimension and phase stability. The “built-in” chain length heterogeneity circumvents the shortcomings encountered by the conventional blending strategy, providing an excellent alternative for quantitatively assessing the effect of molecular symmetry on the self-assembly behaviors of block copolymers.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.2c02529.

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    Cited By

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    This article is cited by 16 publications.

    1. Jinbin Li, Jiayu Xie, Zhanhui Gan, Shuai Wang, Xueyan Feng, An-Chang Shi, Xue-Hui Dong. Effect of Molecular Symmetry on the Self-Assembly Behavior of AB2 Linear–Branched Block Copolymers. Macromolecules 2024, 57 (22) , 10648-10656. https://doi.org/10.1021/acs.macromol.4c02230
    2. Yu-Jung Hsiao, Zi-En Huang, Aditya Sahare, Meng-Zhe Chen, Yu-Hsuan Lin, Hsin-Lung Chen. Accessing the Frank–Kasper Phase of Block Copolymer via Selective Incorporation of Metal Salt. Macromolecules 2024, 57 (22) , 10657-10668. https://doi.org/10.1021/acs.macromol.4c02302
    3. Wei-Chi Chiu, Yu-Hung Cheng, Jin-Hao Lin, Chi-Huan Tung, Taiki Nishimura, Chun-Yu Chen, Takuya Isono, Toshifumi Satoh, Hsin-Lung Chen. Tuning the Complex Spherical Phase of Sugar-Based Block Co-Oligomer via Single-Monomer-Mediated Composition Variation. Macromolecules 2024, 57 (13) , 6076-6089. https://doi.org/10.1021/acs.macromol.4c00439
    4. Shuai Wang, Miao Xu, Zhanhui Gan, Rui Tan, Dongdong Zhou, Xue-Hui Dong. Modular Preparation of Discrete Polyesters through Iterative Growth. Macromolecules 2024, 57 (1) , 272-281. https://doi.org/10.1021/acs.macromol.3c02027
    5. Dongdong Zhou, Miao Xu, Zhanhui Gan, Xiao-Yun Yan, Zhuang Ma, Juncheng Zheng, Xue-Hui Dong. Discrete Diblock Copolymers with Precise Stereoconfiguration. Macromolecules 2023, 56 (5) , 1855-1862. https://doi.org/10.1021/acs.macromol.2c02506
    6. Gang Li, Duohua Jiang, Panpan Ren, Heng Zhao, Kai Zhang, Liping Chang, Zhongguo Liu, Shouzhi Pu. “Clicking” Amphiphilic Block Copolymers onto POSS Core: A General Approach for “Star-like” Polymers with Different Symmetry. Giant 2025, 21 , 100346. https://doi.org/10.1016/j.giant.2024.100346
    7. S. Ercelen Ceylan, B. Bulkurcuoğlu, O. Zaichenko, N. Mitina, Kh. Harhay, N. Finiuk, V.M. Garamus. Polymer-based Nanovesicles. 2024, 153-178. https://doi.org/10.1039/9781837672981-00153
    8. Zhanhui Gan, Zhuoqi Xu, Kun Tian, Dongdong Zhou, Luyang Li, Zhuang Ma, Rui Tan, Weihua Li, Xue-Hui Dong. Stabilizing hexagonally close-packed phase in single-component block copolymers through rational symmetry breaking. Nature Communications 2024, 15 (1) https://doi.org/10.1038/s41467-024-50906-9
    9. Xinyue Zhao, Chenhui Wei, Wang Fuzhou, Xinran Zhang, Jianchuang Wang, Mengfei Wang, Maoxin Zhang, Chunxiu Zhang, Erqiang Chen, Haifeng Yu. Frank–Kasper phases in charge transfer complexes enable tunable photoelectronic properties. Soft Matter 2024, 20 (26) , 5212-5220. https://doi.org/10.1039/D4SM00357H
    10. Xiao-Lin Lyu, Shi-Chu Yang, An-Qi Xiao, Ping-Ping Hou, Wei Zhang, Hong-Bing Pan, Zhi-Hao Shen, Xing-He Fan, Qi-Feng Zhou. Ordered Bicontinuous Network Structures Regulated by Orientational Interactions in a Rod-Coil Block Copolymer. Chinese Journal of Polymer Science 2024, 42 (5) , 636-642. https://doi.org/10.1007/s10118-024-3082-z
    11. Yuxin Liu, Rui Tan, Haibing Wu, Xue-Hui Dong, Zhengbiao Zhang. Quantitative understanding of phase segregation behaviors by precisely building discrete oligo-ester-b-oligo-olefin block copolymers. Science China Chemistry 2024, 67 (3) , 1008-1016. https://doi.org/10.1007/s11426-023-1805-2
    12. Meng-Zhe Chen, Chi-Huan Tung, Chun-Yu Chen, Hsin-Lung Chen. Expanding the window of the Frank-Kasper σ phase of block copolymer/homopolymer blend by selective incorporation of metal salt. Physical Review Materials 2023, 7 (11) https://doi.org/10.1103/PhysRevMaterials.7.115604
    13. Bo Hou, Wen-Bin Zhang, Yu Shao. Unconventional 2D Periodic Nanopatterns Based on Block Molecules. Chinese Journal of Polymer Science 2023, 41 (10) , 1508-1524. https://doi.org/10.1007/s10118-023-3038-8
    14. Roza Szweda. Sequence- and stereo-defined macromolecules: Properties and emerging functionalities. Progress in Polymer Science 2023, 145 , 101737. https://doi.org/10.1016/j.progpolymsci.2023.101737
    15. Bo Hou, Xiaojin Yan, Jinlin He, Wen-Bin Zhang, Yu Shao. Self-assembly of three-component bolaform giant surfactants with branched architectures. Giant 2023, 15 , 100165. https://doi.org/10.1016/j.giant.2023.100165
    16. Jiahao Shi, Xianbo Huang, Weihua Li. The impact of intramolecular polydispersity on the self-assembly of AB n miktoarm star copolymers. Physical Chemistry Chemical Physics 2023, 25 (29) , 20032-20041. https://doi.org/10.1039/D3CP00994G

    Macromolecules

    Cite this: Macromolecules 2023, 56, 3, 833–840
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.2c02529
    Published February 6, 2023
    Copyright © 2023 American Chemical Society

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