Clusters are ensembles of bound atoms intermediate in size between a molecule and a bulk solid. Some of these clusters form stable units with atomically precise structures that give rise to collective behaviours that mimic those of traditional atoms, essentially functioning as ‘superatoms’. Such superatoms are exciting, nanoscale building blocks for materials design. Sustained synthetic and theoretical efforts over the past 40 years have created a vast library of chemically tuneable superatoms that display unique physical and chemical properties. The use of superatoms as building blocks for materials offers opportunities to design materials with tailored functionalities; however, this potential has only begun to be realized in the past few years. The assembly of superatomic crystals presents numerous challenges, including the design of suitable building blocks, control of the self-assembly process, promotion of strong inter-superatom coupling and understanding the resulting collective properties. In this Review, we assess recent advances in meeting these challenges by focusing on metal chalcogenide and carbon-based clusters (for example, fullerenes) as superatomic building blocks.

团簇是键合的原子的集合体，其大小介于分子和整体固体之间。其中一些团簇形成具有原子精确结构的稳定单元，从而产生模仿传统原子行为的集体行为，本质上起着“超原子”的作用。此类超级原子是用于材料设计的令人兴奋的纳米级构建基块。在过去的40年中，经过持续的合成和理论努力，创建了庞大的化学可调谐超原子库，这些库具有独特的物理和化学特性。使用超级原子作为材料的基础材料提供了设计具有定制功能的材料的机会。但是，这种潜力只是在过去几年才开始意识到。超原子晶体的组装提出了许多挑战，包括设计合适的构件，控制自组装过程，促进强上原子间的耦合以及理解由此产生的整体性质。在本综述中，我们将重点放在金属硫族化物和碳基团簇（例如富勒烯）作为超原子的构建基块上，以评估应对这些挑战的最新进展。