Recent progress in dichalcophosphate coinage metal clusters and superatoms

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(47), P. 7182 - 7195

Published: Jan. 1, 2023

Atomically precise clusters of group 11 metals (Cu, Ag, and Au) attract considerable attention owing to their remarkable structure fascinating properties. One the unique subclasses these is based on dichalcophosphate ligands [(RO)2PE2]- type (E = S or Se, R alkyl). These successfully stabilise most diverse Cu, Au superatoms, spanning from simple ones amazing assemblies featuring unusual structural bonding patterns. It noteworthy that such complicated are assembled directly cheap reagents, metal(I) salts anions. This reaction, when performed in presence a hydride other anion sources, foreign metal ions, results hydrido- anion-templated homo- heteronuclear structures. In this feature article, we survey recent advances exciting field, highlighting powerful synthetic capabilities system "a salt - [(RO)2PX2]- templating borohydride" as an inexhaustible platform for creation new atomically clusters, nanoalloys.

Language: Английский

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Anion-templated silver nanoclusters: precise synthesis and geometric structure

Science and Technology of Advanced Materials, Journal Year: 2023, Volume and Issue: 24(1)

Published: April 18, 2023

Metal nanoclusters (NCs) are gaining much attention in nanoscale materials research because they exhibit size-specific physicochemical properties that not observed the corresponding bulk metals. Among them, silver (Ag) NCs can be precisely synthesized only as pure Ag but also anion-templated NCs. For NCs, we expect following capabilities: 1) size and shape control by regulating central anion (anion template); 2) stabilization adjusting charge interaction between surrounding atoms; 3) functionalization selecting type of anion. In this review, summarize synthesis methods influences on geometric structure which include halide ions, chalcogenide oxoanions, polyoxometalate, or hydride/deuteride This summary provides a reference for current state may promote development with novel structures properties.

Language: Английский

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Anion-Directed Assembly of a Bimetallic Pd/Ag Nanocluster: Synthesis, Characterization, and HER Activity

Molecules, Journal Year: 2025, Volume and Issue: 30(2), P. 404 - 404

Published: Jan. 18, 2025

Palladium-doped silver nanoclusters (NCs) have been highlighted for their unique physicochemical properties and potential applications in catalysis, optics, electronics. Anion-directed synthesis offers a powerful route to control the morphology of these NCs. Herein, we report novel Pd-doped Ag NC, [Pd(H)Ag13(S){S2P(OiPr)2}10] (PdHAg13S), synthesized through inclusion sulfide hydride anions. This NC features linear S-Pd-H axis enclosed 4-5-4 stacked arrangement atoms. The distinctive environment was characterized by NMR spectroscopy, total structure determined single-crystal X-ray diffraction (SCXRD) supported computational studies. Mass spectrometry photoelectron spectroscopy (XPS) further confirmed assigned composition. construct exhibits promising hydrogen evolution reaction (HER) activity. Our findings highlight anion-directed creating bimetallic NCs with tailored structures catalytic properties.

Language: Английский

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The first polyoxoniobate-templated silver cluster with temperature-dependent luminescent emission

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(20), P. 2927 - 2930

Published: Jan. 1, 2023

The compound [(Nb6O19)@Ag34(tBuCC)24(CH3COO)2] (Ag34) was synthesized using the solvothermal method combined with volatilization. This first case, to best of our knowledge, isolating a silver cluster containing polyoxoniobate (PONb) template. luminescence, solution behavior and solid-state stability Ag34 were studied in detail. Electrospray ionization mass spectrometry indicated that can maintain integrity its skeleton solution. Detection temperature could be potential application unique luminescent behavior. We expect this work inspire further fabrications PONb-templated high-nuclearity clusters.

Language: Английский

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Molybdate-Templated Luminescent Silver Alkynyl Nanoclusters: Total Structure Determination and Optical Property Analysis

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(17), P. 7631 - 7639

Published: April 16, 2024

Two novel MoO42–-templated luminescent silver alkynyl nanoclusters with 20-nuclearity ([(MoO42–)@Ag20(C≡CtBu)8(Ph2PO2)7(tfa)2]·(tfa–) (1)) and 18-nuclearity ([(MoO42–)@Ag18(C≡CtBu)8(Ph2PO2)7]·(OH) (2)) (tfa = trifluoroacetate) were synthesized the green light maximum emissions at 507 516 nm, respectively. The investigated characterized by single-crystal X-ray crystallography, electrospray ionization mass spectrum (ESI-MS), photoelectron spectroscopy, thermogravimetry (TG), photoluminescence (PL), ultraviolet–visible (UV–vis) density functional theory calculations (DFT). two differ in their structure a supplementary [Ag2(tfa)2] organometallic surface motif, which significantly participates frontier molecular orbitals of 1, resulting similar bonding patterns but different optical properties between clusters. Indeed, both show strong temperature-dependent properties, make them potential candidates fields devices for further applications.

Language: Английский

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Hierarchical assembly of Ag40 nanowheel ranging from building blocks to diverse superstructure regulation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 23, 2024

Achieving precise and controllable hierarchical self-assembly of functional nanoclusters within crystal lattices to create distinct architectures is immense significance, yet it creates considerable challenges. Here we successfully synthesized a silver nanowheel Ag

Language: Английский

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Electrocatalytic and photocatalytic activities of two alkynyl Ag20 cage clusters involved ligand exchange between PhCOO− and CF3COO−

Journal of Saudi Chemical Society, Journal Year: 2024, Volume and Issue: 28(3), P. 101849 - 101849

Published: March 22, 2024

Two silver alkynyl clusters, [(CO32−)@Ag20(tBuC≡C)14(PhCOO)3(CF3COO)] (1) and [(CO32−)@Ag20(tBuC≡C)14(PhCOO)(CF3COO)3] (2), composed of Ag20 shell templated by a CO32− anion supported carboxyl ligands PhCOO− CF3COO−, were synthesized successfully conventional methods. Single crystal X–ray diffractometer (SCXRD) was used to determine the precise structures 1 2. Although compounds 2 have [(CO32−)@Ag20(tBuC≡C)14]4+ unit, numbers CF3COO− along with Ag···Ag interactions affected steric hindrance different their concentrations. That is, separately contain [(CO32−)@Ag20(tBuC≡C)14(PhCOO)(CF3COO)]2+ which is involved in ligand exchange between CF3COO−. Powder X-ray diffraction (PXRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) characterized The photocurrent responses, absorption spectra, as well luminescence been studied. In addition, reduction H2O2 for GCE–1 GCE–2 showed good electrocatalytic activity, catalysts photocatalytic degradation efficiency methylene blue (MB). results suggest that can act new electrocatalysts photocatalysts detect decompose organic pollutants hazardous materials wastewater.

Language: Английский

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Carboxylate Ligand‐supported Ag_n (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(7)

Published: Feb. 14, 2023

Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis their shapes and sizes via anion template-driven one key scientific question. In this work, CO32- templates were captured by [t BuC≡CAg]n system under stimulation induced carboxylate ligand CF3 COO- /PhCOO- , two alkynyl clusters [(CO32- )@Ag21 (t BuC≡C)16 (CF3 COO)3 (H2 O)]⋅DMF⋅2CH2 Cl2 (1) )2 @Ag24 (PhCOO)4 ]⋅CH3 OH⋅4DMF (2) have been successfully isolated charactered. With increase number from single to double, outer atoms twenty-one twenty-four, accompanied growth skeleton 9.8 Å ×6.9 (CO32- unit 10.5 ×7.3 unit. addition, syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, photodegradation compounds 1 2 studied.

Language: Английский

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[MoO₄]²⁻-templatedD_4h-symmetric sandwich Ag₁₃nanocluster coprotected with thiolate and phosphine

Polyoxometalates, Journal Year: 2023, Volume and Issue: 2(2), P. 9140028 - 9140028

Published: May 4, 2023

Mixed-ligand and anion-templated strategies in constructing metal nanoclusters are intricate ingenious processes that face challenges to be studied. Herein, we report a cationic [Ag₁₃(MoO₄)₄(SC₆H₄iPr)₂(dppp)₈]³⁺ (Ag₁₃) nanocluster, which is templated using four [MoO₄]²⁻ anions coprotected by 4-isopropylphenol (iPrC₆H₄S⁻) 1,3-bis (diphenylphosphino) propane (dppp). Two capped (Ag₄SC₆H₄iPr)₂ units connect with the middle Ag@Ag₄ layer via anion templates form three-layer D_4h-symmetric structure. An ideal crystallographic fourfold axis passes through central Ag atom S C atoms of iPrC₆H₄S⁻ ligand. The stacking generates nonface-centered cubic (nonFCC) structure composition Ag₁₃ nanocluster have been fully characterized. In addition, solid ultraviolet–visible (UV–vis) spectra show potential narrow-band-gap semiconductor. photoluminescence (PL) orange-yellow-light emission attributed ligand-to-metal charge transfer. This work has advanced research on shell engineering anionic coprotection assemble high-symmetric nanoclusters.

Language: Английский

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Heterometallic AuI6AgI6 Macrocyclic Cluster Templated by a Supramolecular Melamine Dimer

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(11)

Published: Dec. 12, 2023

The application of supramolecular templates in aligning atomically precise heterometal arrays is important for pursuing functional materials. Herein, we report that a bilayered tri-deprotonated melamine dimer functions as an effective template the construction heterometallic gold(I)-silver(I) macrocyclic cluster [μ

Language: Английский

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