Structurally dynamic crystalline 1D coordination polymers enabled via the Weak-Link Approach
Structurally dynamic crystalline 1D coordination polymers enabled via the Weak-Link Approach
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DOI：
10.1016/j.poly.2022.116116
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发表时间：
2022-09-15
期刊：
影响因子：
2.6
通讯作者：
Mirkin, Chad A.
中科院分区：
文献类型：
--
作者：
Coleman, Benjamin D.;d'Aquino, Andrea I.;Mirkin, Chad A.
超分子化学有潜力用于将动态分子元素赋予配位聚合物，从而可以制备复杂的多功能材料。事实上，超分子化学的弱连接方法（WLA）是一个基于配位化学的平台，可用于设计刺激响应和可切换的纳米级结构。在这里，我们使用 WLA 来设计和合成基于 WLA 的结晶一维配位聚合物。具体来说，封闭的吡啶官能化 WLA 单体复合物与 Cu(BF4)(2).6H(2)O 在乙腈或 N,N-二甲基甲酰胺中反应，产生三个同构 1D 之字形链。通过单晶 X 射线衍射 (SCXRD)、核磁共振 (NMR) 光谱和质谱 (MS) 研究了其中一种聚合物，并研究了其对化学效应物（卤化物离子，Cl-）的响应。重要的是，我们对其中一个模型链的研究显示了构成该模型链的 WLA 复合体的特征结构可切换性。暴露于 Cl- 阴离子后，它会分解成分子成分，包括初始 WLA 复合物的完全开放的同系物。因此，人们可以通过 WLA 单体复合物的结构状态来控制结晶链组装。总而言之，这项工作展示了第一系列基于 WLA 的结晶扩展固体的构建，并代表了构建变构、刺激响应配位聚合物（包括潜在的高阶结构，如金属有机框架）的一种有前景的方法。
Supramolecular chemistry has the potential to be used to impart dynamic molecular elements into coordination polymers so that sophisticated, multifunctional materials can be prepared. Indeed, the Weak-Link Approach (WLA) to supramolecular chemistry is a coordination chemistry-based platform that can be used for the design of stimuli-responsive and switchable nanoscale architectures. Herein, we use the WLA to design and synthesize crystalline, WLA-based 1D coordination polymers. Specifically, the reaction of a closed, pyridine-functionalized WLA monomer complex with Cu(BF4)(2).6H(2)O in acetonitrile or N,N-dimethylformamide yields three isostructural 1D zig-zag chains. One of the polymers was studied via single-crystal X-ray diffraction (SCXRD), nuclear mag-netic resonance (NMR) spectroscopy, and mass spectroscopy (MS), and its response to a chemical effector (halide ion, Cl-) was investigated. Importantly, our investigation of one of the model chains displays the characteristic structural switchability of the WLA complex from which it is comprised. Upon exposure to Cl- anions, it dis-assembles into its molecular components, including the fully-opened congener of the initial WLA complex. Thus, one can control crystalline chain assembly via the structural state of the WLA monomer complex. Taken together, this work has demonstrated the construction of the first series of crystalline WLA-based extended solids and represents a promising method for the construction of allosteric, stimuli-responsive coordination polymers, including potentially higher-ordered structures like metal organic frameworks.