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A Fluorescent Metallacage-cored Supramolecular Polymer Gel Formed by Orthogonal Metal-Coordination and Host-Guest Interactions

机译:正交金属配位和客体-客体相互作用形成的荧光金属环芯超分子聚合物凝胶

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摘要

Herein, we report the preparation of a multi-functional metallacage-cored supramolecular gel by orthogonal metal-coordination and host-guest interactions. A tetragonal prismatic cage with four appended 21-crown-7 (21C7) moieties in its pillar parts was first prepared via the metal-coordination-driven self-assembly of cis-Pt(PEt3)2(OTf)2, tetraphenylethene (TPE) based sodium benzoate ligands and linear dipyridyl ligands. Further addition of a bisammonium linker to the cage delivered a supramolecular polymer network via the host-guest interactions between the 21C7 moieties and ammonium salts, which formed a supramolecular gel at relatively higher concentrations. Due to the incorporation of a TPE derivative as the fluorophore, the gel shows emission properties. Multiple stimuli-responsiveness and good self-healing properties were also observed because of the dynamic metal-coordination and host-guest interactions used to stabilize the whole network structure. Moreover, the storage and loss moduli of the gel are 10-fold of the gel without the metallacage cores, indicating that the rigid metallacage plays a significant role in enhancing the stiffness of the gel. The studies described herein not only enrich the functionalization of fluorescent metallacages via elegant ligand design but also provide a way to prepare stimuli-responsive and self-healing supramolecular gels as robust and smart materials.
机译:在这里,我们报道了通过正交金属配位和宿主-客体相互作用制备多功能金属链核心超分子凝胶。首先通过金属配位驱动的顺式Pt(PEt3)2(OTf)2,四苯乙烯(TPE)的自组装制备了四棱柱形笼,在其柱状部分中具有四个附加的21-crown-7(21C7)部分。基苯甲酸钠配体和线性二吡啶基配体。通过在21C7部分和铵盐之间进行宿主-客体相互作用,向笼中进一步添加双铵连接体,从而形成了超分子聚合物网络,从而形成了相对较高浓度的超分子凝胶。由于掺入了TPE衍生物作为荧光团,该凝胶显示出发射性质。由于用于稳定整个网络结构的动态金属配位和主客体相互作用,还观察到了多种刺激反应性和良好的自愈特性。此外,凝胶的储存和模量是没有金属绷带芯的凝胶的10倍,表明刚性金属绷带在增强凝胶的硬度方面起着重要作用。本文所述的研究不仅通过优雅的配体设计丰富了荧光金属绷带的功能,而且还提供了一种将刺激响应和自我修复的超分子凝胶制备为健壮智能材料的方法。

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