基于主客体识别与互补金属配位构筑超分子聚合物

doi:10.6023/A26060217

摘要/Abstract

受自然界自组装的启发, 金属配位常被用来构建复杂的超分子自组装体系. 然而, 在多组分体系中实现精准、无差错的自组装仍是一项挑战. 本工作研究了三联吡啶互补配体对与金属离子的高选择性金属配位, 并利用此类金属配位与主客体识别之间的协同效应构筑了超分子聚合物. 设计并合成了三种不同的单体A3、CD和EF. 单体A3由三个柱[5]芳烃基团组成, 单体EF含有一个三联吡啶基团和一个中性客体基团, 单体CD则由蒽基取代的三联吡啶和中性客体构成. 在氯仿和丙酮的混合溶剂中, 这三种单体可通过柱芳烃主客体识别和互补金属配位反应自组装形成一种新型超分子聚合物. 综合运用一维和二维核磁共振技术、紫外-可见吸收光谱、荧光光谱、黏度测量和扫描电镜等多种表征手段, 证实了该超分子聚合物的形成. 同时, 由于非共价相互作用的动态可逆特性, 该聚合物对pH及竞争性客体均表现出刺激响应性.

关键词: 主客体相互作用, 互补金属配位, 自组装, 超分子聚合物, 刺激响应性

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

引用此文

王玉珍, 周玉媱, 刘林林, 段钊钊, 徐志豪, 苗田田, 李辉. 基于主客体识别与互补金属配位构筑超分子聚合物[J]. 化学学报, 2026, 84(10): 1626-1632.

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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图/表 8

图1. 单体A3、EF和CD的化学结构, 以及超分子聚合物的构筑示意图

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

图2. 模型化合物1~4的化学结构示意图

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

图3. 核磁共振氢谱(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 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

图4. A3＋EF＋CD＋Zn(OTf)2 的 2D NOESY NMR 谱(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)

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

图5. 紫外-可见吸收滴定实验: (a)将Zn(OTf)2滴加到EF＋CD溶液中(EF的浓度为0.01 mmol/L); (b)将Zn(OTf)2滴加到A3＋EF＋CD的混合溶液中(EF的浓度为0.01 mmol/L). 插图: 加入Zn(OTf)2的浓度与348 nm处吸光度的关系图

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

图6. (a) A3＋EF＋CD＋Zn(OTf)2 的增比黏度随EF浓度的变化关系; (b) A3＋EF＋CD＋Zn(OTf)2 的扩散系数随EF浓度的变化曲线(600 MHz, 293 K)

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)

图7. (a)不同溶液的荧光照片; (b)不同溶液的荧光发射光谱(CDCl3/CD3COCD3, 3/1, V/V, [EF]=0.01 mmol/L)

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)

图8. (a) 365 nm紫外光照射下, 添加TBAOH前后A3＋EF＋CD＋Zn(OTf)2薄膜的照片; (b) A3＋EF＋CD、A3＋EF＋CD＋Zn(OTf)2、A3＋EF＋CD＋Zn(OTf)2＋TBAOH以及A3＋EF＋CD＋Zn(OTf)2＋TBAOH＋TFA溶液在365 nm紫外光照射下的照片

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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