Visible to NIR‐II Photoluminescence of Atomically Precise Gold Nanoclusters

Advanced Materials, Год журнала: 2023, Номер 36(8)

Опубликована: Ноя. 3, 2023

Abstract Atomically precise gold nanoclusters (NCs) have emerged as a new class of precision materials and attracted wide interest in recent years. One the unique properties such pertains to their photoluminescence (PL), for it can widely span visible near‐infrared–I –II wavelengths (NIR‐I/II), even beyond 1700 nm by manipulating size, structure, composition. The current research efforts focus on structure–PL correlation development strategies raising PL quantum yields, which is nontrivial when moving from near‐infrared wavelengths, especially NIR–II regions. This review summarizes progress field, including i) types observed NCs fluorescence, phosphorescence, thermally activated delayed well dual emission; ii) some effective that are devised improve yield (QY) NCs, heterometal doping, surface rigidification, core phonon engineering, with double‐digit QYs NIR horizons; iii) applications luminescent bioimaging, photosensitization, optoelectronics. Finally, remaining challenges opportunities future highlighted.

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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Tailoring gold nanocluster properties for biomedical applications: From sensing to bioimaging and theranostics

Progress in Materials Science, Год журнала: 2023, Номер 142, С. 101229 - 101229

Опубликована: Дек. 12, 2023

Gold nanomaterials have emerged as versatile systems which hold a great promise for several biomedical applications. Among them, gold nanoclusters (AuNCs), ultra-small nanoparticles, gained attention due to their unique optical and electronic properties arising from small size, quantum confinement effects, surface ligands. Their biocompatibility, efficient renal clearance, photoluminescence (PL), catalytic activity make them candidates practical applications, such bioimaging therapy. In this review, we devote our the burgeoning research in area focusing on three main highly intertwined topics. First, present different methods AuNC synthesis alongside key of AuNCs (magnetism, PL). This is followed by description how fine-tune PL property. Lastly, potential applications are discussed detail, with particular focus sensing, bioimaging, nanomedicine.

Язык: Английский

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Noncovalent Interaction Guided Precise Photoluminescence Regulation of Gold Nanoclusters in Both Isolate Species and Aggregate States

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Апрель 23, 2024

Designing luminophores bright in both isolate species and aggregate states is of great importance many emerging cutting-edge applications. However, the conventional either emit but quench state or darken species. Here we demonstrate that precise regulation noncovalent interactions can realize states. It firstly discovered intra-cluster interaction enhances emission atomically Au

Язык: Английский

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Solvent-Mediated Hetero/Homo-Phase Crystallization of Copper Nanoclusters and Superatomic Kernel-Related NIR Phosphorescence

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10767 - 10775

Опубликована: Апрель 9, 2024

Atomically precise superatomic copper nanoclusters (Cu NCs) have been the subject of immense interest for their intriguing structures and diverse properties; nonetheless, variable oxidation state ions complex solvation effects in wet synthesis systems pose significant challenges comprehending crystallization mechanism. Herein, we present a solvent-mediated approach two Cu NCs, namely, Cu26 pure-Cu(I) Cu16. They initially formed as hetero-phase then separated homo-phase via modulating binary solvent composition. In situ UV/vis absorption electrospray ionization mass spectra revealed that assembly was determined to be underlying mechanism hetero/homo-phase crystallization. is 2-electron superatom with kernel-shell structure includes [Cu20Se12]4– shell [Cu6]4+ kernel, containing 1S jellium electrons. Conversely, Cu16 Cu/Se nanocluster features [Cu16Se6]4+ core protected by extra dimercaptomaleonitrile ligands. Remarkably, exhibits unique near-infrared phosphorescence (NIR PH) at 933 nm due presence kernel-related charge transfer (3MM(Cu)CT). Overall, this work not only showcases NCs driven but also enables rare occurrence NIR PH within family.

Язык: Английский

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Triplet–triplet annihilation-based photon upconversion using nanoparticles and nanoclusters

Materials Horizons, Год журнала: 2024, Номер 11(10), С. 2304 - 2322

Опубликована: Янв. 1, 2024

The phenomenon of photon upconversion (UC), generating high-energy photons from low-energy photons, has attracted significant attention. In particular, triplet-triplet annihilation-based UC (TTA-UC) been achieved by combining the excitation states two types molecules, called sensitizer and emitter (or annihilator). With TTA-UC, it is possible to convert weak, incoherent near-infrared (NIR) light, which constitutes half solar radiation intensity, into ultraviolet visible light that are suitable for operation light-responsive functional materials or devices such as cells photocatalysts. Research on TTA-UC being conducted worldwide, often employing with high intersystem crossing rates, metal porphyrins, sensitizers. This review summarizes recent research trends in triplet energy transfer semiconductor nanoparticles nanocrystals diameters nanometer range, also known quantum dots, ligand-protected nanoclusters, have even smaller well-defined sub-nanostructures. Concerning nanoparticles, transmitter ligands applied surface efficiently excitons formed inside emitters. Applications expanding solid-state NIR light. Additionally, there active development sensitizers using more cost-effective environmentally friendly elements. Regarding methods established evaluation excited states, deepening understanding luminescent properties relaxation processes.

Язык: Английский

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Interplay of kernel shape and surface structure for NIR luminescence in atomically precise gold nanorods

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

Опубликована: Авг. 22, 2024

It is challenging to attain strong near-infrared (NIR) emissive gold nanoclusters. Here we show a rod-shaped cluster with the composition of [Au28(p-MBT)14(Hdppa)3](SO3CF3)2 (1 for short, Hdppa N,N-bis(diphenylphosphino)amine, p-MBT 4-methylbenzenethiolate) has been synthesized. Single crystal X-ray structural analysis reveals that it rod-like face-centered cubic (fcc) Au22 kernel built from two interpenetrating bicapped cuboctahedral Au15 units. 1 features NIR luminescence an emission maximum at 920 nm, and photoluminescence quantum yield (PLQY) 12%, which 30-fold [Au21(m-MBT)12(Hdppa)2]SO3CF3 (2, m-MBT 3-methylbenzenethiolate) similar 60-fold Au30S(S‑t‑Bu)18 structure. time-dependent DFT(TDDFT)calculations reveal associated kernel. The small Stokes shift indicates very excited state distortion, leading high radiative decay rate (kr) probability. mixture phosphorescence thermally activated delayed fluorescence(TADF), enhancement mainly due promotion kr rather than inhibition knr. This work demonstrates metal surface structure are both important cluster-based materials. Gold nanoclusters emissions in attain. Here, authors nanoclusters, shape kernal rigid increase emissions.

Язык: Английский

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Recent progress in atomically precise silver nanocluster-assembled materials

Nanoscale, Год журнала: 2024, Номер 16(21), С. 10087 - 10107

Опубликована: Янв. 1, 2024

In the dynamic landscape of nanotechnology, atomically precise silver nanoclusters (Ag NCs) have emerged as a novel and promising category materials with their fascinating properties enormous potential. However, recent research endeavors surged towards stabilizing Ag-based NCs, leading to innovative strategies like connecting cluster nodes organic linkers construct hierarchical structures, thus forming cluster-assembled (CAMs). This approach not only enhances structural stability, but also unveils unprecedented opportunities for CAMs, overcoming limitations individual Ag NCs. this context, review delves into captivating realm nitrogen-based ligand bonded Ag(I)-based providing insights synthetic strategies, structure-property relationships, diverse applications. We navigate challenges advancements in integrating Ag(I) nodes, bound by argentophilic interactions, highly connected periodic frameworks different dimensionalities using linkers. Despite inherent diversity among CAMs demonstrate potential sensing, catalysis, bio-imaging, device fabrication, which all are discussed review. Therefore, gaining insight nanocluster assembly process will offer valuable information, can enlighten readers on design advancement state-of-the-art

Язык: Английский

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Sequential addition of cations increases photoluminescence quantum yield of metal nanoclusters near unity

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

Опубликована: Янв. 11, 2025

Abstract Photoluminescence is one of the most intriguing properties metal nanoclusters derived from their molecular-like electronic structure, however, achieving high photoluminescence quantum yield (PLQY) core-dictated fluorescence remains a formidable challenge. Here, we report efficient suppression total structural vibrations and rotations, management pathways rates electron transfer dynamics to boost near-unity absolute PLQY, by decorating progressive addition cations. Specifically, with sequential Zn 2+ , Ag + Tb 3+ into 3-mercaptopropionic acids capped Au (NCs), low-frequency vibration core progressively decreases 144.0, 55.2 40.0 cm −1 coupling strength electrons-high-frequency related surface motifs gradually diminishes 40.2, 30.5 14.4 meV. Moreover, introducing cation additives significantly reduces time 40, 27 12 ps in pathway staple core. This benefits shrinkage structure that speeds up shell-core transition, particular, provides hopping platform for excited electrons as intrinsic ladder-like energy level structure. As result, it allows remarkable enhancement 51.2%, 83.4%, 99.5%.

Язык: Английский

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Recent progress in atomically precise metal nanoclusters: From bio-related properties to biological applications

Coordination Chemistry Reviews, Год журнала: 2025, Номер 535, С. 216633 - 216633

Опубликована: Март 30, 2025

Язык: Английский

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