Supramolecular Polymer Constructed via host-guest Recognition and Complementary Metal Coordination

doi:10.6023/A26060217

Abstract

In recent years, supramolecular polymers constructed through the synergistic combination of multiple noncovalent interactions have attracted considerable attention in the field of smart materials design owing to their dynamic reversibility and stimulus responsiveness. In this study, three structurally distinct monomers A3, CD, and EF were designed and synthesized. Monomer A3 contains three pillar [5] arene (P5) groups, monomer EF consists of a tripyridine (tpy) group and a neutral guest group (TAPN), and monomer CD comprises an anthracene-substituted tripyridine (atp) group and a neutral guest group (TAPN). In a chloroform/acetone mixed solvent, these monomers self-assemble into a novel supramolecular polymer, driven synergistically by the host-guest recognition between the pillar [5] arene (P5) and the neutral guest (TAPN) and the metal coordination of the tripyridine-based complementary ligand with Zn²⁺. Specifically, a slow exchange process occurs between the pillar [5] arene (P5) and the neutral guest TAPN, while the tripyridine (tpy) and its derivatives form high-fidelity complementary coordination structures in the presence of Zn²⁺, together, these two mechanisms synergistically cross-link the monomers into a polymer network. The successful assembly of this supramolecular polymer was confirmed, and its self-assembly behavior and microscopic morphology were elucidated using a comprehensive array of characterization techniques including ¹H NMR, 2D COSY NMR、2D NOESY NMR, UV-vis, fluorescence spectroscopy, viscosity measurements, and SEM. The results demonstrate that the formation of the supramolecular polymer is concentration-dependent: as the monomer concentration increases, oligomers gradually transform into high-molecular-weight polymers. Benefiting from the dynamic reversibility of noncovalent interactions, the polymer exhibits stimulus responsiveness toward competitive guests and organic bases (or pH changes). Moreover, the atp-Zn²⁺-tpy coordination structure within the supramolecular polymer can induce fluorescence quenching. By employing a synergistic strategy that integrates host-guest recognition and metal coordination, this study not only provides an effective route for constructing supramolecular polymers with novel topological architectures but also lays the foundation for the development of dynamically responsive functional materials.

Key words: host-guest interaction, complementary metal coordination, self-assembly, supramolecular polymer, stimuli-responsiveness

Cite this article

Wang Yuzhen, Zhou Yuyao, Liu Linlin, Duan Zhaozhao, Xu Zhihao, Miao Tiantian, Li Hui. Supramolecular Polymer Constructed via host-guest Recognition and Complementary Metal Coordination[J]. Acta Chimica Sinica, doi: 10.6023/A26060217.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] Yan X.; Wang F.; Zheng B.; Huang F.Chem. Soc. Rev. 2012, 41, 6042.
[2] Li H.; Dong Y.; Li R.; Zhang Y.; Liu S.; Tian, W. Org. Chem. Front.2025, 12, 248.
[3] Zheng B.; Wang F.; Dong S.; Huang, F. Chem. Soc. Rev.2012, 41, 1621.
[4] Wang L.; Cheng L.; Li G.; Liu K.; Zhang Z.; Li P.; Dong S.; Yu W.; Huang F.; Yan X.J. Am. Chem. Soc. 2020, 142, 2051.
[5] Zhang X.; Wang H.; Li P.; Tang H.; Chen T.; Lu W. Smart Mol.2025, 3, e70017.
[6] Li B.; He T.; Shen X.; Tang D.; Yin S. Polym. Chem.2019, 10, 796.
[7] Xu L.; Shen X.; Zhou Z.; He T.; Zhang J.; Qiu H.; Saha M. L.; Yin S.; Stang, P. J. J. Am. Chem. Soc.2018, 140, 16920.
[8] Sheng L.; Liu H.; Hu Z. Q.; Ji, X. F. Chem. Eur. J.2023, 29, e202300990.
[9] Wang Z. Q.; Wang X.; Yang, Y. W. Adv. Mater.2024, 36, 2301721.
[10] Yang M.; Chen S.; Zhang Z.; et al. Nat. Commun.2024, 15, 5760.
[11] Voorhaar L.; Hoogenboom, R. Chem. Soc. Rev.2016, 45, 4013.
[12] Xia D.; Wang P.; Ji X.; Khashab N. M.; Sessler J. L.; Huang F. Chem. Rev.2020, 120, 6070.
[13] Zhang H.; Li J.; Hu Z.; Ji, X. Chin. J. Chem.2024, 42, 2699.
[14] Liu S.; Li H.; Zhang W.; Zhang Y.; Dong Y.; Tian, W. Chin. Chem. Lett.2025, 36, 110465.
[15] Wang Z.; Sun C.; Yang K.; Chen X.; Wang, R. Angew. Chem., Int. Ed.2022, 61, e202206763.
[16] Li Z.; Chen S.; Zhu, J. Adv. Funct. Mater.2024, 34, 2400113.
[17] Liu Y.; Wang L.; Zhao L.; Zhang Y.; Li Z.-T.; Huang, F. Chem. Soc. Rev.2024, 53, 1592.
[18] Lundberg D. J.; Brown C. M.; Bobylev E. O.; et al. Nat. Commun.2024, 15, 3951.
[19] Li Y. F.; Lou X. Y.; Wang C. Y.; Wang Y.; Jia Y.; Lin Q.; Yang Y. W.Chin. Chem. Lett. 2023, 34, 107877.
[20] Wang Z. Q.; Wang X.; Yang, Y. W. Adv. Mater.2024, 36, 2301721.
[21] Jie K. C.; Zhou Y. J.; Yao Y.; Shi B. B.; Huang, F. H. J. Am. Chem. Soc.2015, 137, 10472.
[22] Wei P.; Yan X.; Huang, F. Chem. Soc. Rev.2015, 44, 815.
[23] Rao S.; Wang Y.; Zhang J.-A.; Li L.; Li S.; Liu L.; Xie Y.; Li H.; Tian W. Chem. Sci.2026, 17, 11962.
[24] Li H.; Huang Z.; Huang X.; Huang W.; Rao S.; Liu S.; Zhang Y.; Tian W. Macromolecules2024, 57, 1328.
[25] Wang X.; Zhang J.; Qu J.; Li J.; Feng A.; Liu, J. Chin. J. Chem.2025, 43, 1495.
[26] Xue M.; Yang Y.; Chi X.; Zhang Z.; Huang, F. Acc. Chem. Res.2012, 45, 1294.
[27] Kakuta T.; Yamagishi T. A.; Ogoshi, T. Acc. Chem. Res.2018, 51, 1656.
[28] Liu D.; Mao P.-D.; Zhao L.; Liu T.; Meng, Y.-S. Chin. J. Chem.2025, 43, 1568.
[29] Yan X.; Cook T. R.; Pollock J. B.; Wei P.; Zhang Y.; Yu Y.; Huang F.; Stang, P. J. J. Am. Chem. Soc.2014, 136, 4460.
[30] Han N. X.; Ma J. J.; Yu H.; Shi J. J.; Bai Q. X.; Jiang X.; Zhang Z.; Wang P. S.; Yu J.; Wang M. CCS Chem.2024, 6, 1264.
[31] Shi J.; Li K.; Yu H.; Han N.; Yang T.; Jiang X.; Hao X.-Q.; Chen Z.; Wu G.; Zhang H.; Li B.; Wang, M. Angew. Chem. Int. Ed.2025, 64, e202416150.
[32] Zhang Q.; Tang D.; Zhang J.; Ni R.; Xu L.; He T.; Lin X.; Li X.; Qiu H.; Yin S.; Stang, P. J. J. Am. Chem. Soc.2019, 141, 17909.
[33] Han N.; Jiang X.; Wang M. Chem. Sci.2025, 16, 19532.
[34] Zhu Y.; Zheng W.; Wang W.; Yang, H.-B. Chem. Soc. Rev.2021, 50, 7395.
[35] He Y. J.; Tu T. H.; Su M. K.; Yang C. W.; Kong K. V.; Chan, Y. T. J. Am. Chem. Soc.2017, 139, 4218.
[36] Wang S.-Y.; Fu J.-H.; Liang Y.-P.; He Y.-J.; Chen Y.-S.; Chan, Y.-T. J. Am. Chem. Soc.2016, 138, 3651.
[37] Li C.; Han K.; Li J.; Zhang Y.; Chen W.; Yu Y.; Jia, X. Chem. Eur. J.2013, 19, 11892.
[38] Li Q.; Liu Y.; Liu P.; Shangguan L.; Zhu H.; Shi, B. Org. Chem. Front.2020, 7, 399.
[39] Ding Y.; Wang P.; Tian Y.-K.; Tian Y.-J.; Wang F. Chem. Commun.2013, 49, 5951.
[40] Qian X. M.; Gong W. T.; Li X. P.; Fang L.; Kuang X. J.; Ning, G. L. Chem. Eur. J.2016, 22, 6881.
[41] Chen P. K.; Li Q. C.; Grindy S.; Andersen, N. H. J. Am. Chem. Soc.2015, 137, 11590.

基于主客体识别与互补金属配位构筑超分子聚合物