Atomically precise metal chalcogenide supertetrahedral clusters: frameworks to molecules, and structure to function

Metal chalcogenide supertetrahedral clusters (MCSCs) are of significance for developing crystalline porous framework materials and atomically precise cluster chemistry. Early research interest focused on the synthetic and structural chemistry of MCSC-based porous semiconductor materials with different cluster sizes/compositions and their applications in adsorption-based separation and optoelectronics. More recently, focus has shifted to the cluster chemistry of MCSCs to establish atomically precise structure-composition-property relationships, which are critical for regulating the properties and expanding the applications of MCSCs. Importantly, MCSCs are similar to II-VI or I-III-VI semiconductor nanocrystals (also called quantum dots, QDs) but avoid their inherent size polydispersity and structural ambiguity. Thus, discrete MCSCs, especially those that are solution-processable, could provide models for understanding various issues that cannot be easily clarified using QDs. This review covers three decades of efforts on MCSCs, including advancements in MCSC-based open frameworks (reticular chemistry), the precise structure-property relationships of MCSCs (cluster chemistry), and the functionalization and applications of MCSC-based microcrystals. An outlook on remaining problems to be solved and future trends is also presented. The development of metal chalcogenide supertetrahedral clusters over the past three decades was concentrated in this review, ranging from the construction of cluster-based frameworks to the exploration of atomically precise cluster chemistry.

Automated summary

Metal chalcogenide supertetrahedral clusters (MCSCs) are of great significance for the development of crystalline porous framework materials and atomically precise cluster chemistry. They have attracted research interest in their synthetic and structural chemistry, as well as their applications in different fields. MCSCs have similar properties to semiconductor nanocrystals but avoid their drawbacks, making them suitable for various applications. This review provides a comprehensive overview of three decades of research on MCSCs and highlights their potential in future studies.