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.