Silver(i) chalcogenide/chalcogenolate clusters are promising photofunctional materials for sensing, optoelectronics and solar energy harvesting applications. However, their instability and poor room-temperature luminescent quantum yields have hampered more extensive study. Here, we graft such clusters to adaptable bridging ligands, enabling their interconnection and the formation of rigid metal-organic frameworks. By controlling the spatial separation and orientation of the clusters, they then exhibit enhanced stability (over one year) and quantum yield (12.1%). Ultrafast dual-function fluorescence switching (<1 s) is also achieved, with turn-off triggered by O and multicoloured turn-on by volatile organic compounds. Single-crystal X-ray diffraction of the inclusion materials, obtained by single-crystal-to-single-crystal transformation, enables precise determination of the position of the small molecules within the framework, elucidating the switching mechanism. The work enriches the cluster-based metal-organic framework portfolio, bridges the gap between silver chalcogenide/chalcogenolate clusters and metal-organic frameworks, and provides a foundation for further development of functional silver-cluster-based materials.

Convenient generation of stable superatomic silver clusters and their systematic site-specific tailoring and directional assembly present an enduring and significant challenge. In this work, we prepared a face-centered cubic (fcc) array of Ag superatoms protected by face-capping 1,2-dithiolate-o-carborane (CBHS) ligands, each produced from 1-thiol-o-carborane in crystallization with simultaneous reduction of Ag to Ag. We find that the corner N-donor ligands contribute predominately to the stability and luminescence of the Ag superatom. As the first-formed nanocluster [Ag(CBHS)(CHCN)]·4CHCN (NC-1) with labile vertex-coordinated CHCN ligands is highly unstable, monodendate pyridine ligands were used to replace these CHCN species site-specifically, giving [Ag(CBHS)(pyridine/p-methylpyridine)] (NCs-2,3) in gram scale with its core structure intact, which features ultrastability up to 150 °C in air. Moreover, using bidentate N-containing ligands to bridge the superatomic Ag building blocks, we constructed an unprecedented hierarchical series of 1D-to-3D superatomic silver cluster-assembled materials (SCAM-1,2,3,4), and SCAM-4 is air-stable up to 220 °C. Furthermore, this series of stable solid-state superatomic-nanocluster materials exhibit tunable dual emission with wide-range thermochromism. The present study constitutes a major step toward the development of ligand-modulation of the structure, stability, assembly, and functionality of superatomic silver nanoclusters.

Here, we demonstrate an approach to synthesizing and structurally characterizing three atomically precise anion-templated silver thiolate nanoclusters, two of which form one-and two-dimensional structural frameworks composed of bipyridine-linked nanocluster nodes (referred to as nanocluster-based frameworks, NCFs). We describe the critical role of the chloride (Cl − ) template in controlling the nanocluster's nuclearity with atomic precision and the effect of a single Ag atom difference in the nanocluster's size in controlling the NCF dimensionality, modulating the optical properties, and improving the thermal stability. With atomically precise assembly and size control, nanoclusters could be widely adopted as building blocks for the construction of tunable cluster-based framework materials.

Silver chalcogenolate cluster assembled materials (SCAMs) are a category of promising light-emitting materials the luminescence of which can be modulated by variation of their building blocks (cluster nodes and organic linkers). The transformation of a singly emissive [Ag (SBu ) (CF COO) (bpy) ] (Ag bpy, bpy=4,4'-bipyridine) into a dual-emissive [(Ag (SBu ) (CF COO) (bpy) )] (Ag bpy-2) via cluster-node isomerization, the critical importance of which was highlighted in dictating the photoluminescence properties of SCAMs. Moreover, the newly obtained Ag bpy-2 served to construct visual thermochromic Ag bpy-2/NH by a mixed-linker synthesis, together with dichromatic core-shell Ag bpy-2@Ag bpy-NH -2 via solvent-assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.

Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu81(PhS)46( t BuNH2)10(H)32]3+ (Cu 81 ), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu 81 exhibits extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.

Utilizing aggregation‐induced emission luminogens (AIEgens) as ligands has proven to be an effective strategy for constructing metal–organic frameworks (MOFs) with intense luminescent properties. However, highly luminescent AIEgen‐based MOFs with adjustable emission properties are rarely achieved because of the rigid conformation of AIEgens in the crystalline state. Here, a dual‐node 3D silver chalcogenolate cluster MOF (1) is designed and synthesized, where the AIE ligand shows relatively flexible and rotatable conformations. The conformations of AIE ligands in 1 are switchable by the absorption/desorption of guest molecules. As a result, 1 exhibited not only intense but also guest molecule switched luminescent properties. More importantly, the switching rate is tunable by using different guest molecules. 1 provides a unique visualized prototype to understand the mechanism of guest‐triggered aggregation‐induced emission in MOFs.

Although core–shell copper metal nanoclusters are important emerging materials for practical applications and fundamental scientific research, their synthesis lags behind that of gold and silver nanoclusters–challenged by copper’s much lower half-cell reduction potential, M­(I)/M(0). To overcome this synthetic hurdle, we introduce a simple reaction strategy, involving the mild reducing agent borane tert-butylamine complex, to produce a core–shell superatom copper nanocluster, [Cu61(StBu)26S6Cl6H14]+ (−StBu; tert-butyl thiolate), which is the largest Cu(0)-containing structurally-solved core–shell copper cluster to-date. The nanocluster exhibits a quasi-elongated triangular gyrobicupola (quasi-J 36, J 36 = Johnson solid) Cu19 core and a shell held together by a novel “18-crown-6” metal-sulfide-like belt. Because of its stability, this cluster displays a single molecular ion peak in mass spectrometry measurements without any cluster fragmentation signalsa first observation of its kind for copper nanoclusters that paves the way for researchers to study nanocluster composition, charge, stability, and reaction mechanisms with atomic precision that only mass spectrometry could afford.

Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio‐imaging, cell labeling, phototherapy, and photo‐activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu15(PPh3)6(PET)13]2+, which exhibits bright emission in the near‐infrared (NIR) region (≈720 nm) and crystallization‐induced emission enhancement (CIEE) phenomenon. Single crystal X‐ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu6 core and a, unique among metal clusters, “tri‐blade fan”‐like structure. An in‐depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π‐π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.