Pushing up the Size Limit of Metal Chalcogenide Supertetrahedral Nanocluster

Abstract

The cubic ZnS structure type and the size-dependent properties of related nanoparticles are of both fundamental and technological importance. Yet, it remains a challenge to synthesize large atom-precise clusters of this structure type. Currently, only supertetrahedral clusters with 4, 10, 20, and 35 metal sites (denoted as T2, T3, T4, and T5, respectively) are known. Because the synthesis of T5 in 2002, numerous synthetic efforts targeting larger clusters only resulted in T2-T5 clusters in various compositions and intercluster connectivity, with T6 (56 metal and 84 anion sites) being elusive. Here, we report the so-far largest supertetrahedral cluster (T6, [ZnInS]). New T6 clusters can serve as the host matrix for optically active centers. Mn-doped variants of T4 and T6 have also been made, allowing the investigation of site-dependent Mn emission. The results lead to the elucidation of the mechanism regulating Mn emission via size-dependent crystal lattice strain and provide new insight into Mn-doping chemistry in cluster-based chalcogenides at the atomic level.

Direct observation of charge transfer between molecular heterojunctions based on inorganic semiconductor clusters

“…Crystalline inorganic metal chalcogenides with supertetrahedral clusters (denoted as Tn, where n is the number of metal sites along the tetrahedron edge) serving as SBUs have been extensively investigated because of their fascinating architectures and the effective integration of porosity with semiconducting properties. [27][28][29][30][31][32] Recently, discrete clusters with uniform size and atomically precise crystal lattice structure have been successfully dispersed into cluster-based quantum-dotlike nanoparticles (also called supraclusters) in solvents, and correlations between the cluster structure and function (such as electrochemical, photocatalytic and photoelectric applications) have been established. [33][34][35][36][37] Although the roles of clusters in crystalline open frameworks remain unclear, the signicance of clusters in these frameworks seems to extend beyond the beauty of a symmetrical structure and apparent functionality as nodes for open framework construction.…”

“…For example, precise doping of clusters at the atomic scale allows one to study the synergistic effect of framework heteroatoms on photoluminescence and electrocatalytic properties. 31,34,38 Moreover, the incorporation of multi-metal compositions with various stoichiometric ratios allows one to control the band structure of cluster-based materials for potential applications in photocatalytic pollutant degradation and photocatalytic fuel synthesis. 33,39 From a structural perspective, two types of chalcogenide Tn clusters can co-crystallize into 2D or even 3D frameworks with periodic A-B-A-B arrays.…”

Heterogeneity in Local Chemical Bonding Explains Spectral Broadening in Quantum Dots with Cu Impurities

“…4,[7][8][9][10][11][12]15 This is distinct from Mn doped QDs where Mn transitions localize both carriers. [16][17][18] Consequently, Mn emission can only shift within a small range of the visible spectral window due to changes in local strain environment altering the crystal field splitting energy. 18 Cu impurities, on the other hand, have emission energies that are far more tunable, and extend across the visible and infrared regime making them appealing for a 4 broader range of applications.…”

Atomically Precise Multimetallic Semiconductive Nanoclusters with Optical Limiting Effects

“…[13][14][15][16][17][18] To date,agreat number of noblemetal and semiconductive nanoclusters with atomic precision were reported. [19][20][21][22][23][24][25][26][27][28][29][30][31] Despite such progress,t hese two cluster families are still quite distinct from each other.…”