☆ 4.7 Review

Recent progress in dichalcophosphate coinage metal clusters and superatoms

CHEMICAL COMMUNICATIONS (2023)

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Hydride-containing 2-Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

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Summary: The first hydride-containing 2-electron palladium/copper alloys, PdHCu11 and PdHCu12, were synthesized. X-ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu-11 cuboctahedron and complete Cu-12 cuboctahedron, respectively. PdHCu11 shows excellent HER activity, with an onset potential of -0.05 V (at 10 mA cm(-2)) and consistent HER activity during 1000 cycles in 0.5 M H2SO4.

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Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters

Yu-Rong Ni et al.

Summary: The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)(12)] and [PdHAg20(dtp)(12)](+) are reported. Addition of a single Ag atom to [PdHAg19(dtp)(12)] through the reaction of trifluoroacetic acid yields [PdHAg20(dtp)(12)](+) in 55% yield. Further modification of the shell results in the formation of [PdAg21(dtp)(12)](+) via an internal redox reaction. The interstitial hydride in [PdHAg19(dtp)(12)] and [PdHAg20(dtp)(12)](+) contributes its 1s(1) electron and occupies a PdAg3 tetrahedron.

CHEMISTRY-A EUROPEAN JOURNAL (2023)

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Article Chemistry, Inorganic & Nuclear

Superatom Pruning by Diphosphine Ligands as a Chemical Scissor

Yu-Ming Tseng et al.

Summary: A new method for achieving nanocluster-to-nanocluster transformation was discovered through stepwise synthesis. The added dppm ligands altered the geometry of the nanoclusters and reduced the electron count from eight to two. The resulting compound exhibited strong yellow fluorescence at room temperature.

INORGANIC CHEMISTRY (2023)

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Anion-templated silver nanoclusters: precise synthesis and geometric structure

Yusuke Horita et al.

Summary: Metal nanoclusters (NCs), especially anion-templated Ag NCs, are of great interest in nanoscale materials research due to their size-specific physicochemical properties. The synthesis methods and influences of central anions on the geometric structure of anion-templated Ag NCs, including halide ions, chalcogenide ions, oxoanions, polyoxometalate, or hydride/deuteride, are summarized in this review. This summary serves as a reference for the current status of anion-templated Ag NCs, and may contribute to the development of novel geometric structures and physicochemical properties.

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Interstitial Hydrides in Nanoclusters can Reduce M(I) (M=Cu, Ag, Au) to M(0) and Form Stable Superatoms

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Recent progress in functional atom-precise coinage metal clusters protected by alkynyl ligands

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Self-assembly patterns of non-metalloid silver thiolates: structural, HR-ESI-MS and stability studies

Anastasia Chupina et al.

Summary: Screening of AgNO3/(AgSBu)-Bu-t solutions in DMF, DMSO and NMP led to the isolation of three novel nanosized silver/thiolate complexes with a torus-like core. Structural analysis of two complexes, as well as investigation of their dynamic behavior in CH3CN, revealed the formation of cationic and anionic species driven by a redistribution of (AgNO3) units. Exposure to daylight caused degradation of a complex, resulting in a composite material based on defective orthorhombic Ag2S with porous morphology.

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Homoleptic Silver-Rich Trimetallic M20 Nanocluster

Wei-Jung Yen et al.

Summary: Two silver-rich M-20 alloy nanoclusters were synthesized and fully characterized. The position of Group 11 metals in the clusters was determined, and the presence of Cu-I atoms was found to improve the antioxidation ability.

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Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Tzu-Hao Chiu et al.

Summary: Recent research has found that the encapsulated hydride in hydride-doped noble metal nanoclusters is part of the superatom core, but its precise location has not been experimentally determined. In this study, the position of a four-coordinated hydride in a hydride-doped eight-electron platinum/silver alloy nanocluster was determined for the first time using neutron diffraction.

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Layer-by-layer alloying of NIR-II emissive M50 (Au/Ag/Cu) superatomic nanocluster

Xiao-Hong Ma et al.

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The Factors Dictating Properties of Atomically Precise Metal Nanocluster Electrocatalysts

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A Review of State of the Art in Phosphine Ligated Gold Clusters and Application in Catalysis

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Summary: This review focuses on the unique chemistry, structure, electronic, and optical properties of gold-phosphine clusters, as well as their applications in catalysis. Gold-phosphine clusters have well-defined structures that allow for the study of structure-property relationships. The use of multidentate phosphines enables the preparation of gold clusters with exotic structures beyond regular polyhedra.

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Effects of Single Platinum Atom Doping on Stability and Nonlinear Optical Properties of Ag29 Nanoclusters

Hussein Fakhouri et al.

Summary: This work reports the effects of single platinum atom doping on the optical properties and stability of silver nanoclusters.

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Surface modifications of eight-electron palladium silver superatomic alloys

Subrat Kumar Barik et al.

Summary: This study reports the synthesis and characterization of a series of atomically defined dithio- and diselenophosphate-protected eight-electron superatomic palladium-doped silver nanoclusters, including an unprecedented pair of selenolate-protected isomers. The solid state structures revealed different metal frameworks from the parent cluster due to the distribution of capping silver(I) atoms around a Pd@Ag-12 centered icosahedron with different symmetries. The crystallization of the reaction product led to the co-crystallization of two isomers in the unit cell, a first among selenolate-protected nanoclusters.

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Oxocarbon Anions Templated in Silver Clusters

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Heptanuclear Silver Hydride Clusters as Catalytic Precursors for the Reduction of 4-Nitrophenol

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Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

Guan-Rong Huang et al.

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Compact accumulation of superatomic silver nanoclusters with an octahedral Ag6 core ligated by trithiane

Xun Cheng et al.

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Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Tsubasa Omoda et al.

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Hydrido-coinage-metal clusters: Rational design, synthetic protocols and structural characteristics

Cunfa Sun et al.

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Chemically Modified Gold/Silver Superatoms as Artificial Elements at Nanoscale: Design Principles and Synthesis Challenges

Shinjiro Takano et al.

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A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

Yu-Jie Zhong et al.

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Coinage metal clusters: From superatom chemistry to genetic materials

Baoqi Yin et al.

Summary: The study of metal nanoclusters, especially those of coinage groups, has attracted attention due to the ability to achieve atomic-level precision through experimental and theoretical methods, revealing mechanisms in various nano-catalysts and functional materials. Ligand-protected metal nanoclusters exhibit high catalytic activity and unique selectivity in catalytic reactions, providing information on surface charge states and metal-support interactions.

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Atomically-ordered Trimetallic Superatoms M@Au6Ag6 (M = Pd, Pt): Synthesis and Photoluminescence Properties

Shinjiro Takano et al.

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CHEMISTRY LETTERS (2021)

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Recent advances in polyoxometalate-templated high-nuclear silver clusters

Rui Ge et al.

Summary: The search for feasible strategies to construct high-nuclear silver clusters using anions as templates, such as polyoxometalates (POMs), has attracted continuous interest. POMs have been widely employed to direct the formation of silver clusters and stabilize the final products, showcasing promising applications in various fields.

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Ag(I) symmetrical N,N?-diarylformamidine dithiocarbamate PPh3 complexes: Synthesis, structural characterization, quantum chemical calculations and in vitro biological studies

Segun D. Oladipo et al.

Summary: Three heteroleptic silver(I) dithiocarbamate triphenylphosphine complexes were developed and tested for their antioxidant activity against the DPPH free radical. The complexes showed good antioxidant activity, with compounds 1 and 2 exhibiting better activity compared to ascorbic acid. The complexes were found to be more active against Gram (+) bacteria and showed moderate activity against Gram (-) bacteria, except S. typhimurium. Crystal structures of 2 and 3 were determined, confirming a distorted tetrahedral geometry around the Ag(I) center. Quantum chemical descriptors based on DFT calculations predicted the stability and reactivity of the complexes, showing a clear correlation with their biological activities.

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Synthesis and Luminescence Properties of Two-Electron Bimetallic Cu-Ag and Cu-Au Nanoclusters via Copper Hydride Precursors

Rhone P. Brocha Silalahi et al.

Summary: The synthesis, structural characteristics, and photophysical properties of luminescent Cu-rich bimetallic superatomic clusters were studied. The clusters display similar structures with gold (or silver)-centered Cu-12 cuboctahedra surrounded by dithiocarbamate/dithiophosph(in)ate and alkynyl ligands. Doping Au and Ag atoms into polyhydrido copper nanoclusters significantly enhances their PL quantum yields.

INORGANIC CHEMISTRY (2021)

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Doping effect on the structure and properties of eight-electron silver nanoclusters

Yu-Jie Zhong et al.

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Tzu-Hao Chiu et al.

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Anion templating from a silver(I) dithiophosphate 1D polymer forming discrete cationic and neutral octa- and decanuclear silver(I) clusters

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Anion Encapsulation and Geometric Changes in Hepta- and Hexanuclear Copper(I) Dichalcogeno Clusters: A Theoretical and Experimental Investigation

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[Ag7(H){E2P(OR)2}6] (E = Se, S): Precursors for the Fabrication of Silver Nanoparticles

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Shape Modulation of Octanuclear Cu(I) or Ag(I) Dichalcogeno Template Clusters with Respect to the Nature of their Encapsulated Anions: A Combined Theoretical and Experimental Investigation

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A Nanospheric Polyhydrido Copper Cluster of Elongated Triangular Orthobicupola Array: Liberation of H2 from Solar Energy

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Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus Selenolate

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Octanuclear Cu(I)-dithiophosphates: An Efficient Catalyst System for N-Arylation of Azoles, Amines, and Amides

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Tetrahedral-Shaped Anions as a Template in the Synthesis of High-Nuclearity Silver(I) Dithiophosphate Clusters

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Synthesis and characterization of [Pb{Se2P((OPr)-Pr-i)(2)}(2)](n) pseudo polymorphs: Polymeric, single source precursor enabling preparation of shape-controlled lead selenide structures

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Stable Silver(I) Hydride Complexes Supported by Diselenophosphate Ligands

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Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu8I Cage Inscribed in a S12 Icosahedral Framework

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The CVD of silver selenide films from dichalcogenophosphinato and imidodichalcogenodiphosphinatosilver(I) single-source precursors

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Octanuclear Copper(I) Clusters Inscribed in a Se12 Icosahedron: Anion-induced Modulation of the Core Size and Symmetry

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Atomic and electronic structure of gold clusters:: understanding flakes, cages and superatoms from simple concepts

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Preparation, characterization, and electrophysical properties of nanostructured BiPO4 and Bi2Se3 derived from a structurally characterized, single-source precursor Bi[Se2P(OiPr)2]3

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Synthesis of Sb2Se3 nanowires via a solvothermal route from the single source precursor Sb[Se2P(OiPr)2]3

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Recent advances in the coordination chemistry of diselenophosphates and allied ligands

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Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties

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New halide-centered discrete Agl8 cubic clusters containing diselenophosphate ligands, {Ag8(X)[Se2P(OR)2]6}(PF6) (X = Cl, Br; R = Et, Pr, Or):: Syntheses, structures, and DFT calculations

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Novel chloride-centered discrete CuI8 cubic clusters containing diselenophosphate ligands.: Syntheses and structures of {Cu8(μ8-Cl)[Se2P(OR)2]6}(PF6) (R = Et, Pr, iPr)

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Novel silver diselenophosphate clusters: structures of Ag-10(mu(10) Se)[Se2P(OEt)(2)](8) and {Ag[Se2P(OPri)(2)]}(6)

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A novel nonacoordinate bridging selenido ligand in a tricapped trigonal-prismatic geometry. X-Ray structure of Cu-11(mu(9)-Se)(mu(3)-Br)(3)[Se2P(OPri)(2)](6)

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