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冠醚与铂/钯配合物的构建策略研究进展

Research Progress on Construction Strategies of Crown Ether and Platinum/Palladium Complexes

  • 摘要: 冠醚作为第一代超分子主体,具有可选择性识别配位的柔性腔穴,被广泛作为基础单元构筑超分子配合物。在众多冠醚超分子配合物中,冠醚与中心原子(Pt或Pd)构建的各类型配合物在响应材料、抗癌药物和催化材料等领域被广泛应用。目前,已开发多种冠醚与中心原子构建的超分子配合物,主要包括离子对型配合物、中性分子配合物以及冠醚环外配位配合物等。依赖冠醚腔穴与离子或中性分子间丰富的配位形式,通过离子偶极和氢键等多种相互作用构筑的配合物展现出多种组装策略。本文从组装策略方面综述冠醚与中心原子构建配合物的结构特征,分析配合物的组装驱动力,总结和归纳冠醚与中心原子形成配合物的构建规律。最后,对冠醚和中心原子组成的离子对型配合物、中性分子配合物和冠醚环外配位配合物的构建策略给出建议,并对其在超分子组装领域的发展趋势进行展望,即以简单配合物作为构建单元,可控组装在催化、响应和吸附材料等领域具有潜在应用价值的如轮烷、锁烃、MOF等新型功能化配合物。

     

    Abstract: Crown ether, as the first generation of supramolecular hosts, is widely used as a fundamental building block for constructing supramolecular complexes due to its flexible cavity with selective recognition and coordination. Among the supramolecular complexes of crown ether, various types of complexes constructed by crown ether and central atom (Pt or Pd) are widely used in the fields of response materials, anticancer drugs, and catalytic materials. At present, researchers have developed a variety of supramolecular complexes constructed by crown ethers and central atoms, including ion-pair complexes, and neutral molecular complexes, crown ether exocyclic coordination complexes. Relying on the rich coordination forms between crown ether cavities with ions or neutral molecules, the complexes constructed by various interactions such as ionic dipoles and hydrogen bonds show a variety of assembly strategies. In this paper, the structural characteristics of the complexes constructed by crown ether and central atom were reviewed from the aspect of assembly strategy, and the assembly driving force of the supporting complexes was analyzed. The construction rules of the complexes formed by crown ether and central atom were summarized. Finally, the construction strategies of ion-pair complexes, neutral molecular complexes, and crown ether exocyclic coordination complexes composed of crown ether and central atom were proposed, and their development trends in the field of supramolecular assembly were forecasted, that is, using simple complexes as building units, controllable assembly of new functional complexes such as rotaxane, catenanes, MOF and so on, and has potential applications in the fields of catalysis, response and adsorption materials.

     

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