Synthesis, Structural Characterization, and Electronic Structure Analysis of F-type Superatomic Molecules.

The investigation of bonding interactions between superatoms continues to be a largely unexplored area of study. In this study, we present the synthesis and characterization of two F-type superatomic molecules [AuAg(CHNOS)(DPPB)] and [AuAg(CHNS)(DPPM)] ( and for short, respectively). The overall structures were confirmed via X-ray crystallography, revealing the horizontal expansion of the biicosahedral AuAg yielding [AuAg(CHNOS)(DPPB)] and vertical expansion of the biicosahedral AuAg yielding [AuAg(CHNS)(DPPM)].

[Cu(SeCH)(Dppe)Se] assembled from tetrahedra and octahedra: synthesis, characterization, structure and catalytic properties.

Herein, we successfully synthesized a copper nanocluster, [Cu(SeCH)(Dppe)Se]. The Cu features a tetrahedral Cu core, surrounded by tetrahedral Se and octahedral Cu subunits, and further stabilized by CuSe, Cu(SeR), and DppeCu staples, which can be interpreted as an assembly of tetrahedral and octahedral units. Density functional theory (DFT) calculations were employed to investigate the electronic structure of Cu.

Cu(I)-Glutathione Assembly Supported on ZIF-8 as Robust and Efficient Catalyst for Mild CO Conversions.

The Cu-glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF-8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single-atom Cu(I) catalyst. Synergy between Cu(I) and ZIF-8, revealed by catalytic experiments and DFT calculation, affords CO conversion into high-value-added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency.

An insight, at the atomic level, into the structure and catalytic properties of the isomers of the Cu cluster.

The study of structural isomerism in copper nanoclusters has been relatively limited compared to that in gold and silver nanoclusters. In this work, we present the controlled synthesis and structures of two isomeric copper nanoclusters, denoted as Cu22-1 and Cu22-2, whose compositions were determined to be Cu(SePh)(Se)(P(Ph-F)) through single-crystal X-ray diffraction (SCXRD). The structural isomerism of Cu22-1 and Cu22-2 arises from the different arrangements of a few Cu(SeR)(PR) motifs on the surface structure.

Direct α-Arylation of Benzo[]furans Catalyzed by a Pd Cluster.

As an interim paradigm for the catalysts between those based on more conventional mononuclear molecular Pd complexes and Pd nanoparticles widely used in organic synthesis, polynuclear palladium clusters have attracted great attention for their unique reactivity and electronic properties. However, the development of Pd cluster catalysts for organic transformations and mechanistic investigations is still largely unexploited. Herein, we disclose the use of trinuclear palladium (PdCl) species as an active catalyst for the direct C-H α-arylation of benzo[]furans with aryl iodides to afford 2-arylbenzofurans in good yields under mild conditions.

Mixed-Dimensional Partial Dealloyed PtCuBi/C as High-Performance Electrocatalysts for Methanol Oxidation with Enhanced CO Tolerance.

Developing efficient electrocatalysts for methanol oxidation reaction (MOR) is crucial in advancing the commercialization of direct methanol fuel cells (DMFCs). Herein, carbon-supported 0D/2D PtCuBi/C (0D/2D PtCuBi/C) catalysts are fabricated through a solvothermal method, followed by a partial electrochemical dealloying process to form a novel mixed-dimensional electrochemically dealloyed PtCuBi/C (0D/2D D-PtCuBi/C) catalysts. Benefiting from distinctive mixed-dimensional structure and composition, the as-obtained 0D/2D D-PtCuBi/C catalysts possess abundant accessible active sites.

In-situ synthesis of carbon-supported ultrafine trimetallic PdSnAg nanoparticles for highly efficient alcohols electrocatalysis.

Designing functional and durable electrocatalysts for the oxidation of alcohols plays a significant role for the development of direct alcohol fuel cells (DAFCs). Herein, carbon-supported ultrafine PdSnAg nanoparticles with an average size of 3.27 nm (denoted as PdSnAg/C NPs) have been synthesized for alcohols electrocatalysis.

Bismuth Incorporation in Palladium Hydride for the Electrocatalytic Ethanol Oxidation with Enhanced CO Tolerance.

Introducing nonmetal and oxophilic metal into palladium (Pd)-based catalysts is beneficial for boosting electrocatalysis, especially regarding the improvement of mass activity (MA) and CO tolerance. Herein, the stable bismuth-doped palladium hydride (Bi/PdH) networks have been successfully fabricated through a simple one-step method. The intercalation of interstitial H atoms expands the lattice of Pd, and the doping of oxophilic metal Bi restrains the adsorption of poisonous intermediates on the surface of Pd, thereby improving the activity and durability of the as-prepared catalysts in the ethanol oxidation reaction (EOR).

Ligand-protected metal nanoclusters as low-loss, highly polarized emitters for optical waveguides.

Photoluminescent molecules and nanomaterials have potential applications as active waveguides, but such a use has often been limited by high optical losses and complex fabrication processes. We explored ligand-protected metal nanoclusters (LPMNCs), which can have strong, stable, and tunable emission, as waveguides. Two alloy LPMNCs, PtAg and AuAg (7 ≤ ≤ 9), were synthesized and structurally determined.

Manifestation of the interplay between spin-orbit and Jahn-Teller effects in Au superatom UV-Vis fingerprint spectra.

Atomically precise nanoclusters play an important role in nanoscale catalysis, photonics, and quantum information science. Their nanochemical properties arise from their unique superatomic electronic structures. As the flagship of atomically precise nanochemistry, the Au(SR) nanocluster exhibits tunable spectroscopic signatures that are sensitive to the oxidation state.

Rationally Engineered CYP3A4 Fluorogenic Substrates for Functional Imaging Analysis and Drug-Drug Interaction Studies.

Cytochrome P450 3A4 (CYP3A4) is a key xenobiotic-metabolizing enzyme-mediated drug metabolism and drug-drug interaction (DDI). Herein, an effective strategy was used to rationally construct a practical two-photon fluorogenic substrate for hCYP3A4. Following two-round structure-based substrate discovery and optimization, we have successfully constructed a hCYP3A4 fluorogenic substrate () with desirable features, including high binding affinity, rapid response, excellent isoform specificity, and low cytotoxicity.

Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts.

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C.

Non-directed C-H arylation of electron-deficient arenes by synergistic silver and Pd cluster catalysis.

Transition-metal clusters have attracted great attention in catalysis due to their unique reactivity and electronic properties, especially for novel substrate binding and activation modes at the bridging coordination sites of metal clusters. Although palladium complexes have demonstrated outstanding catalytic performance in various transformations, the catalytic behaviors of polynuclear palladium clusters in many important synthetic methodologies remain much less explored so far. Herein, we disclose the use of an atomically defined tri-nuclear palladium (PdCl) species as a catalyst precursor in Ag(I)-assisted direct C-H arylation with aryl iodides under mild conditions.

Matching Bidentate Ligand Anchoring: an Accurate Control Strategy for Stable Single-Atom/ZIF Nanocatalysts.

Improving metal loading and controlling the coordination environment is nontrivial and challenging for single-atom catalysts (SACs), which have the greatest atomic efficiency and largest number of interface sites. In this study, a matching bidentate ligand (MBL) anchoring strategy is designed for the construction of CuN SACs with tunable coordination environments (Cu loading range from 0.4 to15.

Low Pt-Doped Crystalline/Amorphous Heterophase PdP Nanowires as Efficient Catalysts for Methanol Oxidation.

Pd-based catalysts are attractive anodic electrocatalysts for direct methanol fuel cells owing to their low cost and natural abundance. However, they suffer from sluggish reaction kinetic and insufficient electroactivity in methanol oxidation reaction (MOR). In this work, we developed a facile one-pot approach to fabricate low Pt-doped PdP nanowires with crystalline/amorphous heterophase (termed Pt-PdP NWs) for MOR.

Enhancing Electrocatalytic Methanol Oxidation on PtCuNi Core-Shell Alloy Structures in Acid Electrolytes.

A key challenge for direct methanol fuel cells is the sluggish reaction kinetics, poor anti-CO poisoning ability, and insufficient Pt utilization of platinum-based catalysts during methanol oxidation reaction (MOR). Herein, we report a facile approach for PtCuNi electrocatalysts with adjustable inner and surface configurations. By judiciously controlling the nucleation/growth kinetics, PtCuNi core-shell alloy nanoparticles (PtCuNi-CS NPs) fortified with a Cu-rich core and a Pt-rich shell are obtained.

Atomically Precise Dinuclear Site Active toward Electrocatalytic CO Reduction.

The development of atomically precise dinuclear heterogeneous catalysts is promising to achieve efficient catalytic performance and is also helpful to the atomic-level understanding on the synergy mechanism under reaction conditions. Here, we report a Ni(dppm)Cl dinuclear-cluster-derived strategy to a uniform atomically precise Ni site, consisting of two Ni-N moieties shared with two nitrogen atoms, anchored on a N-doped carbon. By using synchrotron X-ray absorption spectroscopy, we identify the dynamically catalytic dinuclear Ni structure under electrochemical CO reduction reaction, revealing an oxygen-bridge adsorption on the Ni-N site to form an O-Ni-N structure with enhanced Ni-Ni interaction.

Chiral Phosphine-Copper Iodide Hybrid Cluster Assemblies for Circularly Polarized Luminescence.

Chiral chromophores and their ordered assemblies are intriguing for yielding circularly polarized luminescence (CPL) and exploring intrinsic structure-light emission relationships. With the extensively studied chiral organic molecules and inorganic nanoparticle assemblies for the amplified CPL, the assemblies of copper halide hybrid clusters have attracted intensive attention due to their potential efficient CPL. Here, we report robust chiral phosphine-copper iodide hybrid clusters and their layered assemblies in crystalline states for amplified CPL.

Anisotropic Evolution of Nanoclusters from Ag to Ag: Halogen- and Defect-Induced Epitaxial Growth in Nanoclusters.

Halogens have widely served as handles for regulating the growth of nanoparticles and the control of their physicochemical properties. However, their regulatory mechanism is poorly understood. Nanoclusters are the early morphology of nanoparticles and play an important role in revealing the formation and growth of nanoparticles due to their precise structures.

Surface engineering of linearly fused Au units using diphosphine and Cd doping.

Herein, surface engineering was delicately performed to assemble two new Au-Cd alloy nanoclusters, including [Cd2Au17(S-c-C6H11)12(DPPP)2](BPh4) and Cd2Au29(TBBT)17(DPPF)2. Both the Au13 (in Cd2Au17) and Au25 (in Cd2Au29) cores were covered by two identical Au2Cd(SR)6 motifs and two diphosphine ligands. In addition, their optical properties were explored to give clues on the kernel- and surface-dependent electronic structures.

Site-Specific Electronic Properties of [Ag (SR) ] Nanoclusters by X-Ray Spectroscopy.

Silver nanoclusters (NCs) are of significant interest owing to their interesting structural, electronic, and catalytic properties. Among these NCs, Ag (SR) is particularly attractive due to its identical geometry as its Au counterpart, Au (SR) . Herein, the site-specific electronic properties of Ag (SR) and Au (SR) using X-ray spectroscopy experiments and quantum simulations are presented.

Pivotal Electron Delivery Effect of the Cobalt Catalyst in Photocarboxylation of Alkynes: A DFT Calculation.

Photocarboxylation of alkyne with carbon dioxide represents a highly attractive strategy to prepare functionalized alkenes with high efficiency and atomic economy. However, the reaction mechanism, especially the sequence of elementary steps (leading to different reaction pathways), reaction modes of the H-transfer step and carboxylation step, spin and charge states of the cobalt catalyst, etc., is still an open question.

Selective dual detection of HS and Cu by a post-modified MOF sensor following a tandem process.

Fabrication of metal-organic frameworks (MOFs) based multifunctional sensors for various environmental pollutants represents a promising solution to the development of novel monitoring technologies. In this work, a dual responsive sensor of UiO-66-MA has been efficiently fabricated via post-modification of the UiO-66-MOF with maleic anhydride (MA), and dual detection of HS and Cu in aquatic environments has been achieved tandemly. UiO-66-MA could selectively undergo Michael addition with HS accompanying a linear fluorescence turn-on behavior.

A mechanistic study on Cu(i) catalyzed carboxylation of the C-F bond with CO: a DFT study.

The Cu(i) catalyzed carboxylation of the C-F bond recently reported by Yu and co-workers is an excellent method for the construction of complex fluoroacrylate compounds with high regioselectivity. In the present study, theoretical calculations were carried out to investigate the detailed mechanism of the catalytic cycle and the origin of regioselectivity. The calculation results reveal that the overall catalytic cycle proceeds via the migratory insertion of difluoroalkene on the boryl-Cu(i) species, synβ-F elimination, transmetalation, and carboxylation steps.