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 terpyridine (tpy) group and a neutral guest group (TAPN), and monomer CD comprises an anthracene-substituted terpyridine (atp) group and a guest moiety (CN). In a chloroform/acetone mixed solvent, these monomers self-assemble into a novel supramolecular polymer, driven synergistically by the host-guest recognition and the metal coordination of the terpyridine-based complementary ligand with Zn²⁺. Specifically, a slow exchange process occurs between the pillar [5] arene (P5) and the neutral guest TAPN, while the terpyridine (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 nuclear magnetic resonance tests, ultraviolet-visible spectroscopy, fluorescence spectroscopy, viscosity measurements, and scanning electron microscopy. 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

Yuzhen Wang, Yuyao Zhou, Linlin Liu, Zhaozhao Duan, Zhihao Xu, Tiantian Miao, Hui Li. Supramolecular Polymer Constructed via Host-guest Recognition and Complementary Metal Coordination[J]. Acta Chimica Sinica, 2026, 84(10): 1626-1632.

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Fig. & Tab. 8

Figure 1. Chemical structures of monomers A3, EF, and CD, and a schematic diagram of the construction of supramolecular polymer

Figure 2. Schematic diagram of the chemical structures of model compounds 1~4

Figure 3. Nuclear magnetic resonance spectra (400 MHz, CDCl3/CD3COCD3, 3/1, V/V, 298 K, n(A3)∶n(EF)∶n(CD)∶n(Zn(OTf)2)=2∶3∶3∶3, 15 mmol/L): (a) A3＋EF＋CD＋Zn(OTf)2, (b) EF, (c) A3, (d) CD

Figure 4. 2D NOESY NMR spectrum (400 MHz, CDCl3/CD3COCD3, 3/1, V/V, 298 K, n(A3)∶n(EF)∶n(CD)∶n(Zn(OTf)2)=2∶3∶3∶3, 60 mmol/L) of the mixture of A3, EF, CD, and Zn(OTf)2

Figure 5. UV-Vis absorption titration experiment: (a) Zn(OTf)2 was titrated into a solution of EF＋CD (concentration of EF is 0.01 mmol/L); (b) Zn(OTf)2 was titrated into a mixed solution of A3＋EF＋CD (concentration of EF is 0.01 mmol/L). Inset of (a and b) showed normalized absorbance changes at 348 nm, respectively

Figure 6. (a) The specific viscosity of A3＋EF＋CD＋Zn(OTf)2 against the concentration of EF, (b) Diffusion coefficient of A3＋EF＋CD＋Zn(OTf)2 against the concentration of EF (600 MHz, 293 K)

Figure 7. (a) Fluorescence images of different solutions, (b) Fluorescence emission spectra of different solutions (CDCl3/CD3COCD3, 3/1, V/V, [EF]=0.01 mmol/L)

Figure 8. (a) Photographs of the A3＋EF＋CD＋Zn(OTf)2 film before and after the addition of TBAOH under 365 nm UV light, (b) Photographs of A3＋EF＋CD, A3＋EF＋CD＋Zn(OTf)2, A3＋EF＋CD＋Zn(OTf)2＋TBAOH, and A3＋EF＋CD＋Zn(OTf)2＋TBAOH＋TFA solutions under 365 nm UV light irradiation

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