Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization
Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2025-01-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.21.10 |
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| author | Wentao Yu Zhiyao Yang Chengkan Yu Xiaowei Li Lihua Yuan |
| author_facet | Wentao Yu Zhiyao Yang Chengkan Yu Xiaowei Li Lihua Yuan |
| author_sort | Wentao Yu |
| collection | DOAJ |
| description | Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional materials. |
| format | Article |
| id | doaj-art-519a8bcf189f433397aa8b5ef967629d |
| institution | Kabale University |
| issn | 1860-5397 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj-art-519a8bcf189f433397aa8b5ef967629d2025-02-03T09:10:17ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972025-01-0121117918810.3762/bjoc.21.101860-5397-21-10Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerizationWentao Yu0Zhiyao Yang1Chengkan Yu2Xiaowei Li3Lihua Yuan4College of Chemistry, Sichuan University, Chengdu 610064, China College of Chemistry, Sichuan University, Chengdu 610064, China College of Chemistry, Sichuan University, Chengdu 610064, China College of Chemistry, Sichuan University, Chengdu 610064, China College of Chemistry, Sichuan University, Chengdu 610064, China Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional materials.https://doi.org/10.3762/bjoc.21.10hydrogen-bonded macrocycleorthogonal self-assemblyshape-persistentsupramolecular polymer |
| spellingShingle | Wentao Yu Zhiyao Yang Chengkan Yu Xiaowei Li Lihua Yuan Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization Beilstein Journal of Organic Chemistry hydrogen-bonded macrocycle orthogonal self-assembly shape-persistent supramolecular polymer |
| title | Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization |
| title_full | Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization |
| title_fullStr | Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization |
| title_full_unstemmed | Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization |
| title_short | Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization |
| title_sort | hydrogen bonded macrocycle mediated dimerization for orthogonal supramolecular polymerization |
| topic | hydrogen-bonded macrocycle orthogonal self-assembly shape-persistent supramolecular polymer |
| url | https://doi.org/10.3762/bjoc.21.10 |
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