Surface-confined alternating copolymerization with molecular precision by stoichiometric control
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...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-44955-3 |
| _version_ | 1797276410260226048 |
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| author | Lingbo Xing Jie Li Yuchen Bai Yuxuan Lin Lianghong Xiao Changlin Li Dahui Zhao Yongfeng Wang Qiwei Chen Jing Liu Kai Wu |
| author_facet | Lingbo Xing Jie Li Yuchen Bai Yuxuan Lin Lianghong Xiao Changlin Li Dahui Zhao Yongfeng Wang Qiwei Chen Jing Liu Kai Wu |
| author_sort | Lingbo Xing |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-07T15:28:52Z |
| format | Article |
| id | doaj.art-8e732056037247c599bc22cf71fd2646 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-07T15:28:52Z |
| publishDate | 2024-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-8e732056037247c599bc22cf71fd26462024-03-05T16:35:02ZengNature PortfolioNature Communications2041-17232024-01-011511910.1038/s41467-024-44955-3Surface-confined alternating copolymerization with molecular precision by stoichiometric controlLingbo Xing0Jie Li1Yuchen Bai2Yuxuan Lin3Lianghong Xiao4Changlin Li5Dahui Zhao6Yongfeng Wang7Qiwei Chen8Jing Liu9Kai Wu10BNLMS, College of Chemistry and Molecular Engineering, Peking UniversityCenter for Carbon-based Electronics and Key Laboratory for the Physics and Chemistry of Nanodevices, School of Electronics, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityCenter for Carbon-based Electronics and Key Laboratory for the Physics and Chemistry of Nanodevices, School of Electronics, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityBNLMS, College of Chemistry and Molecular Engineering, Peking UniversityAbstract 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.https://doi.org/10.1038/s41467-024-44955-3 |
| spellingShingle | Lingbo Xing Jie Li Yuchen Bai Yuxuan Lin Lianghong Xiao Changlin Li Dahui Zhao Yongfeng Wang Qiwei Chen Jing Liu Kai Wu Surface-confined alternating copolymerization with molecular precision by stoichiometric control Nature Communications |
| title | Surface-confined alternating copolymerization with molecular precision by stoichiometric control |
| title_full | Surface-confined alternating copolymerization with molecular precision by stoichiometric control |
| title_fullStr | Surface-confined alternating copolymerization with molecular precision by stoichiometric control |
| title_full_unstemmed | Surface-confined alternating copolymerization with molecular precision by stoichiometric control |
| title_short | Surface-confined alternating copolymerization with molecular precision by stoichiometric control |
| title_sort | surface confined alternating copolymerization with molecular precision by stoichiometric control |
| url | https://doi.org/10.1038/s41467-024-44955-3 |
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