Copper nanoclusters: emerging photoredox catalysts for organic bond formations DOI Creative Commons
Arunachalam Sagadevan, Kathiravan Murugesan, Osman M. Bakr

и другие.

Chemical Communications, Год журнала: 2024, Номер 60(94), С. 13858 - 13866

Опубликована: Янв. 1, 2024

Advancements in fine chemical synthesis and drug discovery continuously demand the development of new more efficient catalytic systems. In this regard, numerous transition metal-based catalysts have been developed successfully applied industrial processes. However, need for innovative catalyst systems to further enhance efficiency transformations applications persists. Metal nanoclusters (NCs) represent a distinct class ultra-small nanoparticles (<3 nm) characterized by precise number metal atoms coordinated with defined ligands. This structure confers abundant unsaturated active sites unique electronic optical properties, setting them apart from conventional or bulk metals. The well-defined monodisperse nature NCs make particularly attractive applications. Among these, copper-based emerged as versatile sustainable challenging organic bond-forming reactions. Their including natural abundance, accessible oxidation states, diverse ligand architectures, strong photophysical characteristics, contribute their growing prominence field. review, we discuss photocatalytic activities Cu-based nanoclusters, focusing on cross-coupling reactions (C-C C-N), click reactions, multicomponent couplings,

Язык: Английский

Modulating Decarboxylative Oxidation Photocatalysis by Ligand Engineering of Atomically Precise Copper Nanoclusters DOI
Mohammad Bodiuzzaman, Kathiravan Murugesan,

Peng Yuan

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Copper nanoclusters (Cu NCs) characterized by their well-defined electronic and optical properties are an ideal platform for organic photocatalysis exploring atomic-level behaviors. However, potential as greener, efficient catalysts challenging reactions like decarboxylative oxygenation under mild conditions remains unexplored. Herein, we present Cu

Язык: Английский

Процитировано

10
Visible-Light-Induced Excited-State Copper Catalysis: Recent Advances and Perspectives DOI
Nian Li, Bo Li, Kathiravan Murugesan

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 11974 - 11989

Опубликована: Июль 26, 2024

Photoactive copper complexes have gained significant attention due to their photocatalytic activities. Different homogeneous Cu(I) complexes, Cu(II) and heterogeneous copper-based photocatalysts been investigated utilized in a broad spectrum of organic transformations. These applications span radical additions, C–C bond C–heteroatom cross-couplings, aerobic oxidative reactions, kinetic resolutions. This review summarizes the advancements this dynamic field visible-light-induced, excited-state copper-catalyzed reactions over recent years. It is organized according type excited species involved provides perspective on current future developments.

Язык: Английский

Процитировано

9
Machine Learning Potential for Copper Hydride Clusters: A Neutron Diffraction-Independent Approach for Locating Hydrogen Positions DOI

Cong Fang,

Zhuang Wang, Ruili Guo

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 15, 2025

Determining hydrogen positions in metal hydride clusters remains a formidable challenge, which relies heavily on unaffordable neutron diffraction. While machine learning has shown promise, only one deep learning-based method been proposed so far, diffraction data for training, limiting its general applicability. In this work, we present an innovative strategy─SSW-NN (stochastic surface walking with neural network)─a robust, non-neutron diffraction-dependent technique that accurately predicts positions. Validated against copper clusters, SSW-NN proved effective where X-ray or DFT predictions are available. It offers superior accuracy, efficiency, and versatility across different hydrides, including silver alloy systems, currently without any references. This approach not establishes new research paradigm but also provides universal solution localization other fields constrained by sources.

Язык: Английский

Процитировано

1
Polymorphism of [Cu15(PhCH2CH2S)13(PPh3)6][BF4]2 and Double-Helical Assembly of [Cu18H(PhCH2CH2S)14(PPh3)6Cl3]: Origin of Two Chiral Nanoclusters with Triple-Helical Core from Intermediates DOI Creative Commons
Abhijit Nag,

Abdul Mannan Butt,

Moon Young Yang

и другие.

ACS Materials Letters, Год журнала: 2025, Номер 7(2), С. 442 - 449

Опубликована: Янв. 2, 2025

Here, we report the solvent-induced polymorphism in [Cu15(PET)13(TPP)6][BF4]2(Cu15) (TPP = triphenylphosphine, PET 2-phenylethanthiol), and double-helical assembly of [Cu18H(PET)14(TPP)6Cl3] (Cu18) nanocluster (NC) from reaction intermediates. Both copper NCs have an intrinsically chiral triple-stranded helicate metal core, unlike traditional with a polyhedral-based kernel. The structure Cu15 resembles enantiomeric pair unit cell. Moreover, Cu18 has three-layered 3D chirality sandwich constructed sulfur-bridged aligned top-middle-down configuration. Furthermore, NC self-hierarchically assembles into complex double-stranded helix secondary sustained by noncovalent interactions. Electrospray ionization mass spectrometry (ESI-MS), density functional theory (DFT), X-ray photoelectron spectroscopy (XPS) were utilized to validate single-crystal diffraction (SCXRD) data. Overall, this study provides interesting example polymorphism, chirality, hierarchical NCs, allowing for extensive understanding complicated structures at atomic level.

Язык: Английский

Процитировано

0
Toward the Customized Performance on a Supported Au4Ru2 Cluster Catalyst DOI Open Access

Qiang Yuan,

Tianchun Li,

Hongqiao Lin

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Precisely constructing the catalyst structure and composition at atomic level is highly desirable for unexpected properties, but extremely challenging. The success in atomically precise nanochemistry provides an opportunity active site‐tailoring of catalysts toward unique catalysis. Here, monodisperse Au 4 Ru 2 (PPh 3 ) (SC H Ph) 8 clusters are reported that anchored into aerogel as heterogeneous carbonylation process CO hydrogenation coupled with dimethylamine. indeed a performance stage cluster, on which sites cluster act centers to participate synergistic activation reaction , thereby promoting formylation N,N ‐dimethylformamide (DMF), while play decisive role sequent DMF trimethylamine. Notably, can not only exhibit high turnover number performed batch reactor, also show long‐term utilization flowing fixed‐bed system, have been documented previous catalysts.

Язык: Английский

Процитировано

0
Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters DOI Creative Commons
Jiyan Dai, Chuan Shi, Zhixun Zhang

и другие.

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract In the realm of nanomaterials science, precise and controllable synthesis nanoclusters remains a formidable challenge. This study focuses on silver sulfide via halide ion template method, with an in - depth exploration underlying mechanism. By meticulously regulating halogen concentration, reaction solvent, other parameters, diverse array distinct structures has been successfully fabricated characterized at atomic precision level using X-ray single crystal diffraction. The results clearly demonstrate that concentration exerts profound influence structural characteristics clusters. Different ions can trigger formation disparate nucleation sites structures, choice solvent also plays crucial role determining properties

Язык: Английский

Процитировано

0
Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters DOI
Jiyan Dai, Chuan Shi, Zhixun Zhang

и другие.

Journal of Cluster Science, Год журнала: 2025, Номер 36(2)

Опубликована: Март 7, 2025

Язык: Английский

Процитировано

0
Lighting up metal nanoclusters by the H2O-dictated electron relaxation dynamics DOI Creative Commons
Yuan Zhong,

Xue Wang,

Zhou Huang

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 7, 2025

Abstract The modulation of traps has found attractive attention to optimize the performance luminescent materials, while understanding trap-involved photoluminescence management metal nanoclusters greatly lags behind, thus extensively impeding their increasing acceptance as promising chromophores. Here, we report an efficient passivation structural oxygen vacancies in AuAg by leveraging H 2 O molecules, achieving a sensitive color tuning from 536 480 nm and remarkably boosting quantum yield 5.3% (trap-state emission) 91.6% (native-state emission). In detail, favored electron transfer relevant contributes weak trap-state emission, which is capable being restrained molecules taking Au-O Ag-O bonds. This scenario allows dominated native-state emission with faster radiative rate. parallel, can rigidify landscape on hydrogen bonding, enabling suppression electron-optical phonon coupling decelerated non-radiative presented study deepens tailoring properties manipulating surface trap chemistry relaxation dynamics, would shed new light customizable performance.

Язык: Английский

Процитировано

0
Flat-Shaped Copper Nanoclusters with Near-Infrared Absorption for Enhanced Photothermal Conversion DOI Creative Commons
Yanru Yin, Jing Sun,

Jiahe Liu

и другие.

JACS Au, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Atomically precise metal nanoclusters have emerged as a prominent area of research in recent years, yet the majority previous studies primarily concentrated on gold and silver ones. The challenge controlling shape copper order to investigate their relationship properties remains significant concern contemporary scientific research. In this study, we successfully achieved control nanocluster with rare flat oblate structure using combination multiple ligands (trifluoroacetic acid, 4-fluorothiophenol, triphenylphosphine). resulting nanocluster, composition Cu62(4-F-PhS)30(CF3COO)8(PPh3)6H10, features core aspect ratio high 2.6, which is stabilized by attached or bridged onto kernel. Unlike most previously reported nanoclusters, Cu62 exhibits absorption near-infrared range. Density functional theory calculations reveal that main occurrence transitions takes place at equatorial radius core, corresponding radial exciton oscillation caused confinement flattened inner structure, similar plasmon resonance nanoparticles. unique can also promote photothermal conversion efficiency (PCE). temperature cluster solution increases from room around 90 °C just 10 min, achieving PCE approximately 56%. This study not only has potential stimulate further both structures exploration applications but provides model system for investigating between nanomaterials.

Язык: Английский

Процитировано

0
Green catalyst and reagents DOI

Harshita Shakya,

Srasti Yadav,

Akash Kumar

и другие.

Green Chemistry, Год журнала: 2025, Номер unknown, С. 37 - 64

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0