Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C-C Multiple Bond.

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu(TBBT)(TPP)(CHN)H] () (TBBT: 4--butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method.

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry.

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu H PET (PPh ) ] (Cu ; PET: phenylethanethiolate; PPh : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into the surface-defective analog [Cu H PET (PPh ) ] (Cu ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu .

Atomically Precise Defective Copper Nanocluster Catalysts for Highly Selective C-C Cross-Coupling Reactions.

Point defects in nanoparticles have long been hypothesized to play an important role in governing the particle's electronic structure and physicochemical properties. However, single point defects in material systems usually exist with other heterogeneities, obscuring the chemical role of the effects. Herein, we report the synthesis of novel atomically precise, copper hydride nanoclusters (NCs), [Cu H (C H S) (TPP) ] (Cu ; TPP: triphenylphosphine; C H S: o-thiocresol) with a defined defect in the gram scale via a one-pot reduction method.

[CuH(PET)(PPh)Cl] Reveals Surface Vacancy Defects in Ligand-Stabilized Metal Nanoclusters.

Precise identification and in-depth understanding of defects in nanomaterials can aid in rationally modulating defect-induced functionalities. However, few studies have explored vacancy defects in ligand-stabilized metal nanoclusters with well-defined structures, owing to the substantial challenge of synthesizing and isolating such defective metal nanoclusters. Herein, a novel defective copper hydride nanocluster, [CuH(PET)(PPh)Cl] (; PET: phenylethanethiolate; PPh: triphenylphosphine), is successfully synthesized at the gram scale via a simple one-pot reduction method.

[Cu (PPh ) (PET) ] : a Copper Nanocluster with Crystallization Enhanced Photoluminescence.

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 [Cu (PPh ) (PET) ] , 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 Cu core and a, unique among metal clusters, "tri-blade fan"-like structure.

[Ag(1,2-BDT)]: How Square-Pyramidal Building Blocks Self-Assemble into the Smallest Silver Nanocluster.

The emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag(1,2-BDT)] (1,2-BDT = 1,2-benzenedithiolate).

[Cu(PhS)(BuNH)(H)] Reveals the Coexistence of Large Planar Cores and Hemispherical Shells in High-Nuclearity Copper 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.

Assembly of Atomically Precise Silver Nanoclusters into Nanocluster-Based Frameworks.

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.

CsPb Br Single Crystals: Synthesis and Characterization.

CsPb Br is a ternary halogen-plumbate material with close characteristics to the well-reported halide perovskites. Owing to its unconventional two-dimensional structure, CsPb Br is being looked at broadly for potential applications in optoelectronics. CsPb Br investigations are currently limited to nanostructures and powder forms of the material, which present unclear and conflicting optical properties.