Chemical Flexibility of Atomically Precise Metal Clusters

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7262 - 7378

Опубликована: Май 2, 2024

Ligand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging to expand the library of available materials stimulate development new functionalities is becoming increasingly pressing requirement. This Review focuses on origin from structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments metal-to-ligand ratios, thermodynamic effects. In introduction, we briefly outline explain differences commonalities M(I)/M(I/0) coinage clusters. Additionally, distinguish bonding characteristics atoms core, which give rise their distinct flexibility. Section 2 delves into categories, theories related following sections 3 7, primarily elucidate mechanisms trigger flexibility, dynamic processes transformation, resultant alterations structure, ensuing modifications physical–chemical properties. 8 presents notable applications have emerged utilizing assemblies. Finally, section 9, discuss future challenges opportunities within this area.

Язык: Английский

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Molecule-like synthesis of ligand-protected metal nanoclusters

Nature Reviews Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 5, 2024

Язык: Английский

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Labile Ligands Protected Cu₅₀ Nanoclusters with Tailorable Optical Limiting Effect

ACS Materials Letters, Год журнала: 2023, Номер 6(1), С. 281 - 289

Опубликована: Дек. 19, 2023

Atomically precise copper nanoclusters have recently attracted tremendous attention, as they often exhibit structures and properties distinct to their gold silver counterparts. Although considerable progress has been made in the preparation structure determination of nanoclusters, introduction those newly created materials more underlying areas such nonlinear optics is its infancy. Herein, we report a new class Cu50 exhibiting tunable optical limiting effect. The facile prototype reported this work allows discovery up four clusters with nearly identical metal framework, namely, Cu50(CF3COO)12(3,5-diMe-PhS)18(PPh3)4H2 (Cu50-1), Cu50(CF3COO)10(4-F-PhS)20(PPh3)6H2 (Cu50-2), Cu50(CF3COO)10(PhS)20(PPh3)6H2 (Cu50-3), Cu50(PhCOO)10(4-F-PhS)20(PPh3)6H2 (Cu50-4). molecular series, revealed by X-ray single crystal analysis, describes stabilization Cu44 core an organometallic shell thiolate-carboxylate-phosphine-copper. combinatorial studies electrospray ionization mass spectroscopy (ESI-MS), nuclear magnetic resonance (NMR), density functional theory (DFT) calculations suggest that contain 18 free valence electrons, making them probably first library superatoms featuring 18e. As nanosecond Z-scan measurements results, typical effects, indicating promising applications field (NLO). More importantly, labile surface motifs on allow us tune NLO properties. This not only reports atomically process, clear structures, but also encourages research exploration exciting areas.

Язык: Английский

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Site-Recognition-Induced Structural and Photoluminescent Evolution of the Gold–Pincer Nanocluster

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 9631 - 9639

Опубликована: Март 26, 2024

The induced structural transformation provides an efficient way to precisely modulate the fine structures and corresponding performance of gold nanoclusters, thus constituting one important research topics in cluster chemistry. However, driving forces mechanisms these processes are still ambiguous many cases, limiting further applications. In this work, based on unique coordination mode pincer ligand-stabilized nanocluster Au8(PNP)4, we revealed site-recognition mechanism for transformations nanoclusters. "open nitrogen sites" surface interact with different inducers including organic compounds metals trigger conversion Au8(PNP)4 Au13 Au9Ag4 respectively. Control experiments verified mechanism, femtosecond nanosecond transient absorption spectroscopy electronic photoluminescent evolution accompanied by transformation.

Язык: Английский

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Dithiocarbonate-Protected Au₂₅ Nanorods of a Chiral D₅ Configuration and NIR-II Phosphorescence

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12734 - 12742

Опубликована: Апрель 9, 2024

Innovative surface-protecting ligands are in constant demand due to their crucial role shaping the configuration, property, and application of gold nanoclusters. Here, unprecedented O-ethyl dithiocarbonate (DTX)-stabilized atomically precise nanoclusters, [Au25(PPh3)10(DTX)5Cl2]2+ (Au25DTX-Cl) [Au25(PPh3)10(DTX)5Br2]2+ (Au25DTX-Br), were synthesized structurally characterized. The introduction bidentate DTX not only endowed nanocluster with unique staggered Au25 nanorod configurations but also generated symmetry breaking from D5d geometry kernels chiral D5 configuration molecules. chirality nanorods was notably revealed through single-crystal X-ray diffraction, separation induced by employing ligands. nanorods, as opposed eclipsed ones, responsible for large red shift emission wavelengths, giving rise a promising near-infrared II (NIR-II, >1000 nm) phosphorescence. Furthermore, performances photocatalytic sulfide oxidation electrocatalytic hydrogen evolution reactions have been examined, it has demonstrated that outstanding catalytic activity nanoclusters is highly related stability.

Язык: Английский

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Eight‐Electron Copper Nanoclusters for Photothermal Conversion

Chemistry - A European Journal, Год журнала: 2024, Номер 30(28)

Опубликована: Март 12, 2024

Owing to distinct physicochemical properties in comparison gold and silver counterparts, atomically precise copper nanoclusters are attracting embryonic interest material science. The introduction of cluster nanomaterials more interesting fields is currently urgent desired. Reported this work novel [XCu

Язык: Английский

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Tuning Electrocatalytic Water Oxidation Activity: Insights from the Active‐Site Distance in LnCu₆ Clusters

Small, Год журнала: 2024, Номер 20(32)

Опубликована: Март 22, 2024

Abstract Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of catalytic reaction and exploring complex relationship between structure activity. Herein, three series water‐soluble heterometallic LnCu 6 , abbreviated ‐AC (Ln = La, Nd, Gd, Er, Yb; HAC acetic acid), ‐IM La Nd; IM Imidazole), ‐IDA H 2 IDA Iminodiacetic acid) are presented, each featuring uniform metallic core stabilized by distinct protected ligands. Crystal analysis reveals triangular prism topology formed six Cu 2+ ions around one Ln 3+ ion in with variations Cu···Cu distances attributed to different Electrocatalytic oxygen evolution (OER) shows that these exhibit OER activities remarkable turnover frequency 135 s −1 NdCu 79 32 . Structural Density Functional Theory (DFT) calculations underscore correlation shorter improves activity, emphasizing pivotal role active‐site distance regulating electrocatalytic activities. These results provide valuable insights into contribute design efficient homogeneous electrocatalysts.

Язык: Английский

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Photochemical Route for Synthesizing Atomically Precise Metal Nanoclusters from Disulfide

Nano Letters, Год журнала: 2023, Номер 23(16), С. 7508 - 7515

Опубликована: Июль 21, 2023

Practical approaches to the synthesis of atomically precise metal nanoclusters are in high demand as they provide structural basis for investigating nanomaterials' structure-property correlations with atomic precision. The Brust-Schiffrin method has been widely used, while essential reductive ligands (e.g., thiols) limit application this synthesizing specific frameworks and surface ligands. In work, we developed a photochemical route by applying disulfide, which is available, stable, environmentally friendly sulfur source. This enables construction structurally diverse especially features PhS-protected that were not easily achieved previously gram-scale synthesis. A reduction-oxidation cascade mechanism revealed route. work expected open up new opportunities nanocluster will contribute practical applications kind nanomaterial.

Язык: Английский

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Monodispersed and Monofunctionalized DNA‐Caged Au Nano‐Clusters with Enhanced Optical Properties for STED Imaging

Small, Год журнала: 2024, Номер 20(29)

Опубликована: Фев. 22, 2024

The performance of Stimulated Emission Depletion (STED) microscopy depends critically on the fluorescent probe. Ultrasmall Au nanoclusters (Au NCs) exhibit large Stokes shift, and good stimulated emission response, which are potentially useful for STED imaging. However, NCs polydispersed in size, sensitive to surrounding environment, difficult control surface functional group stoichiometry, results reduced density high heterogeneity labeling biological structures. Here, this limitation is overcome by developing a method encapsulate ultrasmall with DNA cages, yielded monodispersed, monofunctionalized that long-term stable. Moreover, DNA-caging also greatly improved fluorescence quantum yield photostability NCs. In imaging, DNA-caged ≈40 nm spatial resolution able resolve microtubule line shapes homogeneity. contrast, without caging, NCs-DNA conjugates only achieved ≈55 spotted, poorly resolved structures, due presence aggregates. Overall, developed achieve precise functionalization improve monodispersity, stability, as well optical properties NCs, providing promising class probes

Язык: Английский

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A Cages‐on‐Cluster Structure Constructed by Post‐Clustering Covalent Modifications and Guest‐Enabled Stimuli‐Responsive Luminescence

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Май 7, 2024

A gold(I)-cluster-based twin-cage has been constructed by post-clustering covalent modification of a hexa-aldehyde cluster precursor with triaminotriethylamines. The cages-on-cluster structure double cavities and four binding sites, which show site-discriminative for silver(I) copper(I) guests. guests in the tripodal hats affect luminescence cluster: tetra-silver(I) host-guest complex is weakly red-emissive, while bis-copper(I)-bis-silver(I) one non-emissive but stimuli-responsive supramolecule. ion inside tri-imine cavity oxidation sensitive, enables release bright emissive triggered H

Язык: Английский

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