Fabricating sub-nanometer materials through cluster assembly

The self-assembly of clusters provides a feasible approach for the bottom-up fabrication of functional materials with tailored properties. Sub-nanometer cluster assembly with a well-defined construction presents a precisely controllable structure and extraordinary properties, which provides an ideal model for the investigation of structures and properties at the molecular level. Non-covalent interactions between clusters may dominate the assembly behavior, appearing as tunable structures different from their nano-counterparts. Interactions between clusters and their superatom orbitals can significantly influence the electronic structures, because of which exceptional properties may emerge. In this paper, recent progress on cluster-based assemblies is introduced, including sub-nanometer building blocks of noble metal and polyoxometalate (POM) clusters. The structures, formation mechanism and properties of these cluster assemblies are discussed from experimental and theoretical aspects. This perspective aims to provide a new insight into the design and manufacture of sub-nanometer materials based on clusters.