Cluster-assembled materials based on polyoxometalates (POMs) process unprecedented structural tunability and polymer-like behaviors because of the sub-nanometer-sized building blocks and their non-covalent linkage. Through the whole journey in their development, exquisite POM cluster assemblies with advanced functions spring up, and the control over their nanostructures tends to be more precise and reach their nature at molecular level. In this paper, recent progress in cluster-assembled materials based on POMs is overviewed, including the assembly of covalently and non-covalently modified POM clusters as well as the co-assembly of POM clusters and inorganic entities. By surfactant encapsulation, POM clusters are compatible in various solvents, and hybrid assemblies with diverse morphologies and unique properties have been achieved. The Janus POM-POSS clusters feature intricate assemblies in mixed solvent systems, which provide instructive understanding for solution behaviors of macro-ions. Notably, the POM clusters can also intervene in the nucleation of nanocrystals, resulting in the formation of cluster-nuclei co-assembled materials with well-organized structures and wide-ranging composition compatibility. Meanwhile, the chemistry of cluster-assembled materials has not been well explored, and there are great potentials as well as challenges that lie ahead.

基于多金属氧酸盐（POM）的簇组装材料由于具有亚纳米级的结构单元及其非共价键，因此可处理前所未有的结构可调性和类似聚合物的行为。在其整个开发过程中，具有先进功能的精美POM簇组件不断涌现，对其纳米结构的控制趋于更加精确，并在分子水平上达到其本质。本文概述了基于POM的簇组装材料的最新进展，包括共价和非共价修饰的POM簇的组装以及POM簇和无机实体的共组装。通过表面活性剂的封装，POM团簇可在各种溶剂中相容，并且已经实现了具有多种形态和独特性能的混合组件。Janus POM-POSS簇在混合溶剂系统中具有复杂的装配体，为大离子的溶液行为提供了有益的理解。值得注意的是，POM团簇也可以干预纳米晶体的成核，从而形成具有良好组织的结构和广泛的组成相容性的团簇-核共组装材料。同时，团簇组装材料的化学性质尚未得到很好的探索，存在巨大的潜力和挑战。导致形成具有良好组织的结构和广泛的组成相容性的簇核共组装材料。同时，团簇组装材料的化学性质尚未得到很好的探索，存在巨大的潜力和挑战。导致形成具有良好组织的结构和广泛的组成相容性的簇核共组装材料。同时，团簇组装材料的化学性质尚未得到很好的探索，存在巨大的潜力和挑战。