Department of Chemistry, Tsinghua University, Beijing 100084, P.R. China.
Dalton Trans. 2012 Sep 7;41(33):9832-45. doi: 10.1039/c2dt30470h. Epub 2012 Jul 16.
Polyoxometalates (POMs) are discrete anionic metal-oxide nanoclusters which exhibit unrivalled structural diversity, exceptional physical properties, and have many potential applications. Nonetheless, possessing high crystalline energy and hydrophilic nature, the assembly of POM clusters into rationally design architectures has been a long-standing bottleneck for their ultimate use in advanced materials and devices. To confront this challenge, both covalent and non-covalent modifications of POM nanoclusters are increasingly considered. This perspective reviews recent progress in the assembly of non-covalently modified surfactant-encapsulated POM nanoclusters with particular emphasis on our research work. The described solution-based assembly approach provides an excellent control on size, shape, and stability of the assembly structures. By effective exploitation of non-covalent interactions between the POM hybrid nanobuilding blocks, several unprecedented assembly structures including disks, cones, tubes, fullerene-like spheres, multiple shape flowers, wires, and thin films can be achieved. The assembly structures are highly robust and tunable in terms of size and shape and can act as hosts for guest nanomaterials to develop composite materials of combinatorial properties. In the last section of this manuscript, we present the catalytic properties of the assembly structures and their remote controlled manipulation in the reaction system.
多金属氧酸盐（POMs）是离散的阴离子金属氧化物纳米团簇，具有无与伦比的结构多样性、出色的物理性质，并且具有许多潜在的应用。尽管如此，由于具有高结晶能和亲水性，将 POM 簇组装成合理设计的结构一直是其在先进材料和设备中最终应用的长期瓶颈。为了应对这一挑战，人们越来越多地考虑对 POM 纳米簇进行共价和非共价修饰。本综述重点介绍了我们的研究工作，回顾了近年来非共价修饰的表面活性剂包裹的 POM 纳米簇的组装方面的最新进展。所描述的基于溶液的组装方法可以极好地控制组装结构的尺寸、形状和稳定性。通过有效利用 POM 杂化纳米构建块之间的非共价相互作用，可以实现包括盘、锥、管、类富勒烯球体、多种形状的花、线和薄膜在内的几种前所未有的组装结构。组装结构在尺寸和形状上具有高度的稳定性和可调性，并且可以作为客体纳米材料的主体，以开发具有组合性质的复合材料。在本文的最后一节中，我们介绍了组装结构的催化性能及其在反应体系中的远程控制操作。
