Comprehensive and practical guidelines for reduction synthesis of atomically precise coinage-metal nanoclusters

Polyoxometalates, Год журнала: 2024, Номер 4(2), С. 9140075 - 9140075

Опубликована: Авг. 7, 2024

As a model system for studying the structure-and-property relationship and surface coordination chemistry of metal nanomaterials, ligand-stabilized atomically precise coinage-metal (Au, Ag, Cu) nanoclusters have attracted bolstering attention. Considerable effort has been extended to synthesis structure determination in past decades, which chemical reduction high-valence ions presence protective ligands lays foundation. After analyzing over 200 synthetic examples individual prepared by direct method, with reactants either single kind Au, Cu or alloying (e.g., Au-Ag, Au-Pt), as well phosphines, thiolates, alkynyls, N-heterocyclic carbenes, halides their combinations, we propose comprehensive practical guidelines nanoclusters. This Review seeks elucidate prospective introduction robust prototypes engineering nanoclusters, evolved from one-phase, two-phase, miscible solution solid-state synthesis. Several factors are key optimization, mainly including selection precursors, reductant systems, purification strategies. providing an expansive critical viewpoint on this rapidly evolving field, some promising trends future prospected end.

Язык: Английский

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Loading Lewis Acid/Base Pair on Metal Nanocluster for Catalytic Ugi Reaction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Сен. 13, 2024

Constructing structurally robust and catalytically active metal nanoclusters for catalyzing multi-component reactions is an interesting while challenging task. Inspired by Lewis acid base catalysis, we realized the combination of both sites on surface a stable gold nanocluster Au

Язык: Английский

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Atomically Engineered Trimetallic Nanoclusters Toward Enhanced Photoluminescence and Photoinitiation Activity

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

Abstract Precise doping is of vital significance for atomic engineering and the establishment structure‐property relationships in nanocluster (NC) chemistry. Herein, two novel trimetallic MAu 18 Cd 3 (M = Pd/Pt) NCs that are derived from M‐doped Au 25 templates 24 reported, which central M atom surface‐motif atoms concurrently achieved. Compared to original templates, Cd‐induced surface enhances rigidity structural framework enlarges HOMO‐LUMO gaps , significantly improving photoluminescent efficiency by suppressing nonradiative relaxation. The critical role (Pd/Pt) dopant photoluminescence, regulates rate radiative decay excited‐state electrons, has also been substantiated. More notably, doped case PtAu exhibits excellent photoinitiation activity 3D two‐photon printing with a high resolution ≈140 nm, may be attributed prolonged excited state. Overall, this work provides generalized routine precise synthesis multi‐metal concurrent enhancements photoluminescence activity, expected stimulate further research design preparation multi‐functional, NCs.

Язык: Английский

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Pincer-Ligand-Stabilized Group 10 Metal Nanoclusters: Chirality and Boat–Chair Structural Transformation

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 2942 - 2949

Опубликована: Март 13, 2025

Atomically precise metal nanoclusters bridge the gap between atoms and nanoparticles, providing an ideal platform for correlating macroscopic properties of nanoparticles to their microstructures. In comparison rapid development coin nanoclusters, knowledge on group 10 is relatively limited because active nature, resulting in synthetic challenge. this work, we successfully synthesize three that is, Ni3(SNS)3, Ni3(SNOS)3, Pd3(SNS)3, by using SNS pincer ligands, which well-stabilize nickel palladium kernels. Intrinsic chirality originated from asymmetric arrangement surface ligands discovered. Oxidation-induced irreversible transformation boat-like Ni3(SNS)3 chair-like Ni3(SNOS)3 observed, boat/chair structure-dependent reactivity revealed. The structural features intriguing Ni3 Pd3 stabilized ligand will inspire further research nanoclusters.

Язык: Английский

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Cobalt-kernelled icosahedral gold nanocluster

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111230 - 111230

Опубликована: Апрель 1, 2025

Язык: Английский

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Imidazolyl Phosphine as Versatile Hemilabile Ligand: Synthesis and Characterization of a New Tetracationic Au₂₀ Nanocluster

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Май 29, 2025

Abstract As the new type of molecular catalysts, hemilabile ligand‐protected Au nanoclusters hold greater promise in realizing a better trade‐off between catalytic activity and structural stability. Despite large amount (co‐)protected by organic nitrogen ligands, little has been known about those containing dynamically labile Au─N bonds, where ligands are solely limited to pyridyl‐phosphine. In this study, we chose imidazolyl‐phosphine (dpim) as main protecting ligand synthesized tetracationic cluster [Au 20 6 (dppe) 2 Cl ] 4+ ( ‐S , dppe = Ph P(CH ) PPh ), which was structurally characterized crystallographically, spectroscopically, computationally. Albeit similar electronic structure core, possesses different arrangements positive charges from its two reported analogues, thus they may serve an ideal triad for comparatively studying ligand/charge effect on their activities. This work proved potential imidazolyl phosphine versatile syntheses NCs with bonds. The imidazolyl‐phosphines more amenable derivatizations, provides opportunity further enriching library potentially performance.

Язык: Английский

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Unprecedented stacking-dependent piezoluminescence enhancement in atomically precise superatomic gold nanoclusters

Science Advances, Год журнала: 2025, Номер 11(22)

Опубликована: Май 30, 2025

Deciphering the structure-property relationship between cluster stacking and high-efficiency luminescence of metal nanoclusters is crucial for designing synthesizing high-performance light-emitting materials devices. Here, we successfully synthesized two polymorphic gold (Au 8 -C Au -P) investigated their stacking-dependent piezoluminescence based on hydrostatic pressure. Under compression, exhibits notable enhancement. However, -P presents monotonic quenching. High-pressure structural characterizations confirm existence anisotropic compression in -P. high pressure, columnar-stacked shrinks faster along a axis, increasing aspect ratio (AR) fusiform core. layered compressed c reducing AR leading to flatter femtosecond transient absorption, time-resolved photoluminescence, Raman spectra collaboratively that differentiated notably suppresses nonradiative loss caused by low-frequency vibrations core, which responsible enhancement -C.

Язык: Английский

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A Phosphorescent Silver-Copper Nanocluster with a Saddle-Like Stabilizing Surface

Journal of Cluster Science, Год журнала: 2025, Номер 36(4)

Опубликована: Июнь 2, 2025

Язык: Английский

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Controlling Chirality and Stability of Gold Nanoclusters by PNP Pincer Ligand Diastereomers

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Июнь 4, 2025

The emerging metal nanoclusters with atomically precise structures have gained considerable attention because they exhibit promising applications in various fields and serve as ideal models for studying the structure-property correlation of nanoparticles. Despite significant advances, it is still unclear how ligand diastereomers impact stability chirality nanoclusters. In this work, we systematically studied construction gold using PNP (PNP = 2,6-bis(1-(diphenylphosphaneyl)ethyl)pyridine) pincer consisting multiple stereoisomers. A metastable Au6 skeleton was found to be a key intermediate, which can controlled aspects by selectively produce Au9(R,R-PNP)4, Au9(S,S-PNP)4, Au9(R,S-PNP)4, Au6(R,S-PNP)2(R,R-PNP), Au6(R,S-PNP)2(S,S-PNP) intriguing properties such self-sorting spontaneous resolution. This work provides strategy regulating diastereomers.

Язык: Английский

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Multicolor reversible fluorescence of cellulosic gold nanoclusters via pH-triggered ligand recombination

Chemical Engineering Journal, Год журнала: 2024, Номер 503, С. 158388 - 158388

Опубликована: Дек. 9, 2024

Язык: Английский

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