Clickable Norbornene-Based Zirconium Carboxylate Polyhedra
Clickable Norbornene-Based Zirconium Carboxylate Polyhedra
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DOI：
10.1021/acs.chemmater.2c03252
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发表时间：
2023-02-28
影响因子：
8.6
通讯作者：
Cook，Timothy R.
中科院分区：
文献类型：
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作者：
Pastore，Vincent J.;Sullivan，Meghan G.;Cook，Timothy R.
修饰金属-有机多面体（MOPs）性质的一种常用方法是在有机桥接配体上安装垂坠官能团。然后，这些组可以参与耦合反应，以进一步修饰给定的体系结构。通过利用点击化学，可以访问共享共同核心的各种MOPs库，这可以降低合成复杂性和成本。本文报道了富马酸和二氯化锆（Cp2ZrCl2）通过一锅串联配位驱动的自组装/ Diels-Alder反应，形成了反应性降冰片烯基MOP。随后由马来酸和Cp2ZrCl2合成的降冰片烯基Zr簇证明了该串联工艺的普遍性。我们演示了使用多功能巯基点击化学对该笼进行组装后修饰，从而形成了单个功能化的MOPs或交联聚合物/ MOPs杂化复合材料。这些复合材料的物理性能可以通过添加聚（乙二醇）二丙烯酸酯作为共聚物来控制，从而在MOP负载30-60% （w/w）的情况下合成独立的柔性薄膜。这些结果证明了巯基点击化学作为一种MOP功能化方法的有效性，为新型先进材料的合成扩展了工具箱。
A common way to modify the properties of metal–organic polyhedra (MOPs) is to install pendant functionalities on the organic bridging ligands. These groups can then participate in coupling reactions to further decorate a given architecture. Via exploitation of click chemistry, it is possible to access a diverse library of MOPs that share a common core, which can reduce both synthetic complexity and cost. Herein, we report the formation of a reactive norbornene-based MOP through a one-pot tandem coordination-driven self-assembly/Diels–Alder reaction between fumaric acid and zirconocene dichloride (Cp2ZrCl2). The generality of this tandem process was illustrated by the subsequent synthesis of a norbornene-based Zr cluster formed from maleic acid and Cp2ZrCl2. We demonstrate post-assembly modification of this cage using versatile thiol–ene click chemistry, resulting in the formation of either individual functionalized MOPs or cross-linked polymer/MOP hybrid composites. The physical properties of these composites can be controlled by the addition of poly(ethylene glycol) diacrylate as a co-monomer, allowing for the synthesis of free-standing, flexible films at MOP loadings of 30–60% (w/w). These results demonstrate the effectiveness of thiol–ene click chemistry as a method of MOP functionalization, expanding the toolbox for the synthesis of new advanced materials.