Doping‐Mediated Energy‐Level Engineering of M@Au₁₂ Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Май 24, 2022

We synthesized a series of MAu12 (dppe)5 Cl2 (MAu12 ; M=Au, Pd, Pt, Rh, or Ir; dppe=1,2-bis(diphenylphosphino)ethane), which have icosahedral M@Au12 superatomic cores, and systematically investigated their electronic structures, photoluminescence (PL) photocatalytic properties. The energy gap between the highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO) was expanded when doping an M element positioned at lower left periodic table. PL quantum yield enhanced with increase in HOMO-LUMO reached 0.46-0.67 for (M=Pt, Ir) under deaerated conditions. bright PLs from were assigned to phosphorescence based on quenching by O2 . acted as more efficient stable photocatalyst than Au13 intramolecular [2+2] cycloaddition bisenone via oxidative cycle. This study provides rational guides designing photoluminescent gold superatoms heterometal elements.

Язык: Английский

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Body-Centered-Cubic-Kernelled Ag₁₅Cu₆ Nanocluster with Alkynyl Protection: Synthesis, Total Structure, and CO₂ Electroreduction

Journal of the American Chemical Society, Год журнала: 2022, Номер 145(6), С. 3401 - 3407

Опубликована: Дек. 21, 2022

While atomically monodisperse nanostructured materials are highly desirable to unravel the size- and structure-catalysis relationships, their controlled synthesis atomic-level structure determination pose challenges. Particularly, copper-containing precise alloy nanoclusters potential catalyst candidates for electrochemical CO2 reduction reaction (eCO2RR) due high abundance tunable catalytic activity of copper. Herein, we report total an alkynyl-protected 21-atom AgCu nanocluster [Ag15Cu6(C≡CR)18(DPPE)2]-, denoted as Ag15Cu6 (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene; DPPE: 1,2-bis(diphenylphosphino)ethane). The single-crystal X-ray diffraction reveals that consists Ag11Cu4 metal core exhibiting a body-centered cubic (bcc) structure, which is capped by 2 Cu atoms, Ag2DPPE motifs, 18 alkynyl ligands. Interestingly, cluster exhibits excellent eCO2RR with CO faradaic efficiency (FECO) 91.3% at -0.81 V (vs reversible hydrogen electrode, RHE), much higher than (FECO: 48.5% -0.89 vs RHE) Ag9Cu6 bcc structure. Furthermore, shows superior stability no significant decay in current density FECO during long-term operation 145 h. Density functional theory calculations reveal de-ligated can expose more space pair dual metals efficient active sites formation.

Язык: Английский

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Near‐Infrared Light‐Driven Photocatalysis with an Emphasis on Two‐Photon Excitation: Concepts, Materials, and Applications

Advanced Materials, Год журнала: 2023, Номер 36(5)

Опубликована: Сен. 13, 2023

Efficient utilization of sunlight in photocatalysis is widely recognized as a promising solution for addressing the growing energy demand and environmental issues resulting from fossil fuel consumption. Recently, there have been significant developments various near-infrared (NIR) light-harvesting systems artificial photosynthesis photocatalytic remediation. This review provides an overview most recent advancements NIR light through creation novel nanostructured materials molecular photosensitizers, well modulating strategies to enhance processes. A special focus given emerging two-photon excitation photocatalysis. The unique features limitations different are critically evaluated. In particular, it highlights advantages utilizing compared UV-visible irradiation one-photon excitation. Ongoing challenges potential solutions future exploration light-responsive also discussed.

Язык: Английский

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Tailoring Carbon Tails of Ligands on Au₅₂(SR)₃₂ Nanoclusters Enhances the Near-Infrared Photoluminescence Quantum Yield from 3.8 to 18.3%

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(48), С. 26328 - 26338

Опубликована: Ноя. 20, 2023

One of the important factors that determine photoluminescence (PL) properties gold nanoclusters pertain to surface. In this study, four Au52(SR)32 feature a series aromatic thiolate ligands (-SR) with different bulkiness at para-position are synthesized and investigated. The near-infrared (NIR) (peaks 900-940 nm) quantum yield (QY) is largely enhanced decrease in ligand's para-bulkiness. Specifically, capped least bulky p-methylbenzenethiolate (p-MBT) exhibits highest PLQY (18.3% room temperature non-degassed dichloromethane), while Au52 bulkiest tert-butylbenzenethiolate (TBBT) only gives 3.8%. large enhancement QY fewer methyl groups on implies nonradiative decay via multiphonon process mediated by C-H bonds. Furthermore, single-crystal X-ray diffraction (SCXRD) comparison Au52(p-MBT)32 Au52(TBBT)32 reveals lead stronger interligand π···π stacking core, thus restricting ligand vibrations rotations. emission nature identified be phosphorescence thermally activated delayed fluorescence (TADF) based PL lifetime, 3O2 quenching, temperature-dependent absorption studies. 1O2 generation efficiencies for NCs follow same trend as observed performance. Overall, highly NIR-luminescent nanocluster revealed mechanisms expected find future applications.

Язык: Английский

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pH-sensitive phosphorescence in penicillamine-coated Au22 nanoclusters: Theoretical and experimental insights

Chemical Engineering Journal, Год журнала: 2024, Номер 495, С. 153608 - 153608

Опубликована: Июнь 29, 2024

Язык: Английский

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Dynamic surface reconstruction of individual gold nanoclusters by using a co-reactant enables color-tunable electrochemiluminescence

Chemical Science, Год журнала: 2024, Номер 15(9), С. 3255 - 3261

Опубликована: Янв. 1, 2024

We report for the first time phenomenon of continuously color-tunable ECL from individual Au NCs confined in a porous hydrogel matrix. The property arises dynamic surface reconstruction and co-reactants.

Язык: Английский

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Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C–C Multiple Bond

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16295 - 16305

Опубликована: Май 30, 2024

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design development bond-forming reaction based on copper NCs are still in early stages. Herein, we report synthesis atomically nanocluster with a planar core unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), yield via one-pot reduction method. The resulting structurally well-defined Cu45 is highly efficient catalyst for hydroboration alkynes alkenes. Mechanistic studies show that single-electron oxidation situ-formed ate complex enables formation boryl-centered radicals under mild conditions. This work demonstrates promise as C–B heteroatom reactions. compatible wide range alkenes functional groups producing hydroborated products.

Язык: Английский

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Composition‐Dependent Enzyme Mimicking Activity and Radiosensitizing Effect of Bimetallic Clusters to Modulate Tumor Hypoxia for Enhanced Cancer Therapy

Advanced Materials, Год журнала: 2022, Номер 34(31)

Опубликована: Июнь 10, 2022

Abstract Alloying is an efficient chemistry to tailor the properties of metal clusters. As a class promising radiosensitizers, most previously reported clusters exhibit unitary function and cannot overcome radioresistance hypoxic tumors. Here, atomically precise alloy Pt 2 M 4 (M = Au, Ag, Cu) are synthesized with bright luminescence adequate biocompatibility, their composition‐dependent enzyme mimicking activity radiosensitizing effect explored. Specifically, only Au cluster displays catalase‐like activity, while others do not have clusterzyme properties, its highest among all tested. By taking advantage sustainable production O via decomposition endogenous H , modulates tumor hypoxia as well increases efficacy radiotherapy. This work thus advances alloying strategy produce multifunctional therapeutic agents for improving therapy.

Язык: Английский

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Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Z-scheme heterojunctions with enhanced photocatalytic hydrogen production

Nano Research, Год журнала: 2024, Номер 17(6), С. 5002 - 5010

Опубликована: Фев. 29, 2024

Язык: Английский

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NIR-II emissive anionic copper nanoclusters with intrinsic photoredox activity in single-electron transfer

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 1, 2024

Abstract Ultrasmall copper nanoclusters have recently emerged as promising photocatalysts for organic synthesis, owing to their exceptional light absorption ability and large surface areas efficient interactions with substrates. Despite significant advances in cluster-based visible-light photocatalysis, the types of transformations that can catalyze remain limited date. Herein, we report a structurally well-defined anionic Cu 40 nanocluster emits second near-infrared region (NIR-II, 1000−1700 nm) after photoexcitation conduct single-electron transfer fluoroalkyl iodides without need external ligand activation. This photoredox-active efficiently catalyzes three-component radical couplings alkenes, iodides, trimethylsilyl cyanide under blue-LED irradiation at room temperature. A variety fluorine-containing electrophiles nucleophile be added onto an array including styrenes aliphatic olefins. Our current work demonstrates viability using readily accessible metal establish photocatalytic systems high degree practicality reaction complexity.

Язык: Английский

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