Metal Chalcogenide Supertetrahedral Clusters: Synthetic Control over Assembly, Dispersibility, and Their Functional Applications.

ConspectusMetal chalcogenide supertetrahedral clusters (MCSCs) bear the closest structural resemblance to II-VI or I-III-VI semiconductor nanocrystals and can be considered as well-defined ultrasmall "quantum dots" (QDs). Compared to traditional colloidal QDs that are typically associated with size dispersity, irregular surface atomic structures, poorly defined core-ligand interfaces, and random defect/dopant sites, the nano- or subnano-sized MCSCs feature precise structural properties such as atomically uniform size, precise structure, and ordered dopant distribution, all of which offer ample opportunities for a broad and in-depth understanding of the correlation between the precise local structure and site- or size-dependent properties, which are critical to the exploitation of their functional applications. Our previous Account in 2005 provided a narrative on the efforts to expand the structural diversity of open-framework materials using different-sized and compositionally tunable clusters as building blocks with a primary objective of integrating the semiconducting properties with porosity in zeolite-type solids. Over the past 15 years, significant progress has been made, particularly in the synthetic control of discrete clusters, allowing the establishment of the composition-structure-property correlation of the MCSCs to guide the optimization of their properties for various applications. In the present Account, the recent progress in MCSC-based chemistry is reviewed from three aspects: (1) controllable synthesis of new members and types of MCSC models and the development of organic-ligand-directed hybrid assembly modes for MCSC-based open frameworks; (2) new synthetic strategies for the discretization of MCSCs in crystal lattice and their dispersibility in solvents, affording practical applications of pure inorganic MCSCs as nanomaterials; and (3) functionality of MCSC-based materials including photochemical and electrochemical properties triggered by precise dopant/defect sites, open-framework-related functional expansion via host-guest chemistry, and dispersed cluster-based composite materials with synergy from functional multimetallic components. All these advances show that MCSCs with well-defined structures and atomically precise dopant/defect sites are powerful model systems for establishing the precise structure-composition-property correlation and understanding the photophysical dynamic behaviors, both of which are difficult or impossible to achieve in the traditional QD system. Perspectives on their potential applications are presented in terms of the amorphous assemblies of monodispersed MCSCs, MCSC-based two-dimensional layered materials, and optical/electronic devices.