Effect of Ni‐Doping on the Optical, Structural, and Electrochemical Properties of Ag29 Nanoclusters DOI Creative Commons
Abdullah Ahmed Ali Ahmed, Shana Havenridge, Koustav Sahoo

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 24, 2024

Abstract Atomically precise metal nanoclusters (NCs) can be compositionally controlled at the single‐atom level, but understanding structure‐property correlations is required for tailoring specific optical properties. Here, impact of Ni atom doping on optical, structural, and electrochemical properties atomically 1,3‐benzene dithiol (BDT) protected Ag 29 NCs studied. The Ni‐doped (NiAg 28 12 ) NCs, are synthesized using a co‐reduction method characterized electrospray ionization mass spectrometry (ESI MS), ion mobility (IMS), X‐ray photoelectron spectroscopy (XPS). Only single achieved despite changing precursor concentration. in exhibits enhanced thermal stability, electrocatalytic oxygen evolution reaction (OER) compared to parent NCs. Density functional theory (DFT) calculations predict geometry NiAg DFT also used study systematic effect metals such as Au, Cu, Pt into suggests that with Pt, d atomic orbitals contribute creating superatomic orbitals, which not seen other dopants or cluster. emission mechanism dominated by charge transfer from ligands core cluster regardless dopant.

Language: Английский

Triplet–triplet annihilation-based photon upconversion using nanoparticles and nanoclusters DOI Creative Commons
Yoshiki Niihori,

Taiga Kosaka,

Yuichi Negishi

et al.

Materials Horizons, Journal Year: 2024, Volume and Issue: 11(10), P. 2304 - 2322

Published: Jan. 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.

Language: Английский

Citations

10
Triplet-Mediator Ligand-Protected Metal Nanocluster Sensitizers for Photon Upconversion DOI

Daichi Arima,

Shion Hidaka,

So Yokomori

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16630 - 16638

Published: May 13, 2024

Triplet–triplet annihilation photon upconversion (TTA-UC) is attracting a great deal of attention as viable approach to exploit unutilized wavelengths light in solar-driven devices. Recently, ligand-protected metal nanoclusters have emerged compelling platform for serving triplet sensitizers TTA-UC. In this study, we developed an atomically precise, triplet-mediator ligand (TL)-protected nanocluster, Au2Cu6(S-Adm)6[P(DPA)3]2 (Au2Cu6DPA; S-Adm = 1-adamanthanethiolate, DPA 9,10-diphenylanthracene). Au2Cu6DPA, the excitation Au2Cu6 core rapidly generates metal-to-ligand charge transfer state, followed by formation long-lived state (approximately 150 μs) at site TL. By combining Au2Cu6DPA with annihilator, achieved red-to-blue quantum yield (ΦUCg) 20.7 ± 0.4% (50% max.) low threshold intensity 36 mW cm–2 640 nm. This almost reaches maximum limit achievable using annihilator and establishes record-setting value, outperforming previously reported nanocrystal nanocluster sensitizers. Furthermore, strong emission based on pseudo-first-order TTA process was observed under 1 sun illumination, indicating that sensitizer holds promise applications solar-energy-based systems.

Language: Английский

Citations

10
Isomeric Effects of Au28(S-c-C6H11)20 Nanoclusters on Photoluminescence: Roles of Electron-Vibration Coupling and Higher Triplet State DOI Creative Commons
Abhrojyoti Mazumder, Kang Li, Zhongyu Liu

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(32), P. 21534 - 21543

Published: Aug. 2, 2024

The exploration of near-infrared photoluminescence (PL) from atomically precise nanoclusters is currently a prominent area interest owing to its importance in both fundamental research and diverse applications. In this work, we investigate the (NIR) mechanisms two structural isomers gold 28 atoms protected by cyclohexanethiolate (CHT) ligands, i.e., Au28i(CHT)20 Au28ii(CHT)20. Based on their structures, analysis 3O2 (triplet oxygen) quenching nanocluster triplet states, temperature-dependent photophysical studies, theoretical calculations, have elucidated intricate processes governing these isomeric nanoclusters. For Au28i(CHT)20, emission characteristics are identified as phosphorescence plus thermally activated delayed fluorescence (TADF) with PL quantum yield (PLQY) 0.3% dichloromethane under ambient conditions. contrast, Au28ii(CHT)20 isomer exhibits exclusive PLQY 3.7% Theoretical simulations reveal larger singlet (S1)–triplet (T1) gap Au28ii than that Au28i, higher T2 state plays critical role isomers' processes. insights derived investigation not only contribute more profound comprehension principles underlying but also provide avenues for tailoring optical properties

Language: Английский

Citations

4
Enhancement of Photoluminescence Quantum Yield of Silver Clusters by Heavy Atom Effect DOI Creative Commons

A. Akiyama,

Sakiat Hossain, Yoshiki Niihori

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract Many ligand‐protected metal clusters exhibit phosphorescence at room temperature. However, strategies for improving their quantum yield, a critical parameter of performance, remain poorly developed. In contrast, fluorescent dyes are commonly modified by introducing heavy atoms, such as iodine (I), to enhance intersystem crossing in the excited state, thereby harnessing atom effect increase efficiency. this study, pair silver (Ag) is successfully synthesized with internal cavities encapsulating anions (X z − ), namely sulfide ions (S 2− ) or iodide (I which significantly differ atomic number each other. Single‐crystal X‐ray diffraction and nuclear magnetic resonance spectroscopy revealed that resulting Ag composed X@Ag 54 S 20 (thiolate) (sulfonate) m , where (X, = (S, 12) (I, 11). photoelectron atoms these compounds mixed‐valence state. Furthermore, experiments on photoluminescence central anion induced an heavy‐atom similar observed organic dyes. As result, yield became 16 times higher when replaced I atom.

Language: Английский

Citations

0
Recent progress in atomically precise metal nanoclusters: From bio-related properties to biological applications DOI Creative Commons
Lizhong He, Tingting Dong, De‐en Jiang

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 535, P. 216633 - 216633

Published: March 30, 2025

Language: Английский

Citations

0
Tailoring sensitization properties and improving near-infrared photon upconversion performance through alloying in superatomic molecular Au25 nanoclusters DOI
Masaaki Mitsui,

Yuki Miyoshi,

Daichi Arima

et al.

Nanoscale, Journal Year: 2024, Volume and Issue: 16(31), P. 14757 - 14765

Published: Jan. 1, 2024

Noble-metal nanoclusters (NCs) protected by organic ligands have recently come to the forefront as potent triplet sensitizers for photon upconversion (UC) via triplet-triplet annihilation (TTA), owing their capacity atomic-level photophysical property customization. Among these, rod-shaped bi-icosahedral [Au25(PPh3)10(S-C2H4Ph)5Cl2]2+ (Au-rod) NC is a particularly iconic superatomic molecular NC, identified near-infrared (NIR)-absorbing sensitizer TTA-UC. In this study, we synthesized Cu-doped NCs, [Au25-xCux(PPh3)10(S-C2H4Ph)5Cl2]2+ (AuCu-rod), and paired them with 9,10-bis(phenylethynyl)anthracene (BPEA) annihilator/emitter explore impact of Cu-doping on sensitization NIR-UC performance. The state AuCu-rod, lifetime 3 μs, exhibited modest blue shift compared Au-rod, resulting in increment driving force energy transfer (TET) BPEA acceptor. TET rate constant was determined be 5.0 × 107 M-1 s-1, which an order magnitude higher than Au-rod/BPEA pair. This improvement has led remarkable increase efficiency. Notably, AuCu-rod/BPEA pair facilitated efficient UC 805 nm NIR light into 510 visible light, realizing large anti-Stokes close 0.9 eV. internal quantum yield combination 2.33 ± 0.05%, marking fivefold enhancement over Au-rod (0.49%). Thus, alloying offers promising route enhance performance tuning optimizing compatibility between annihilator. Additionally, series experiments, formation small amounts microaggregates observed. These aggregates did not undergo singlet fission could retain multiple long-lived excitons. characteristic TTA among excitons, NIR-to-visible emission.

Language: Английский

Citations

2
Recent Advances in Understanding Triplet States in Metal Nanoclusters: Their Formation, Energy Transfer, and Applications in Photon Upconversion DOI
Masaaki Mitsui

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: unknown, P. 12257 - 12268

Published: Dec. 5, 2024

Recent experimental findings, rapidly accumulating over the past few years, has revealed that in electronic excited states of metal nanoclusters (MNCs) composed noble atoms (e.g., Cu, Ag, or Au), triplet are generated with remarkably high efficiency, exerting a pivotal influence photophysical properties MNCs, notably their photoluminescence characteristics. As result, MNCs increasingly recognized as promising luminescent nanomaterials exhibit room-temperature phosphorescence and thermally activated delayed fluorescence. Furthermore, significance triplet-state-mediated energy transfer charge intermolecular processes is gaining increasing recognition, particularly applications photosensitizers for singlet oxygen organic molecular triplets. This Perspective focuses on recent advances understanding formation photophysics MNCs. Additionally, brief overview provided series studies exploring use sensitizers photon upconversion via triplet-triplet annihilation, future prospects this emerging application discussed.

Language: Английский

Citations

2
Triplet Energy Transfer and Photon Upconversion from Metal Nanocluster with Near‐Unity NIR Emission Quantum Yield DOI
Linlin Zeng, W. M. Shi, Jie Kong

et al.

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 29, 2024

Abstract Metal nanoclusters have emerged as new triplet sensitizers of photo‐upconversion, while the strategy engineering their electronic properties for efficient utilization energy remains elusive. Au 16 Cu 6 ( t BuPhC≡C) 18 (Au ) metal nanocluster shows near‐unity near‐infrared (NIR) phosphorescent quantum yield at room temperature and intersystem crossing yield, which is an ideal platform understanding mechanism transfer (TET). Here, a model system designed to probe TET from different organic acceptors obtained k Stern–Volmer plots. Transient absorption spectroscopy clearly formation T 1 signals in molecules accompanied by decay , indicates direct mechanism. Among four molecules, between perylene possesses highest yield. Moreover, relatively small threshold intensity 0.4 W cm −2 with 532 nm excitation large anti‐Stokes shift 0.68 eV 635 triplet‐triplet annihilation (TTA) upconversion (UC). The UC underlying will pave way optimizing performance expanding optoelectronic devices.

Language: Английский

Citations

1
Effect of Ni‐Doping on the Optical, Structural, and Electrochemical Properties of Ag29 Nanoclusters DOI Creative Commons
Abdullah Ahmed Ali Ahmed, Shana Havenridge, Koustav Sahoo

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 24, 2024

Abstract Atomically precise metal nanoclusters (NCs) can be compositionally controlled at the single‐atom level, but understanding structure‐property correlations is required for tailoring specific optical properties. Here, impact of Ni atom doping on optical, structural, and electrochemical properties atomically 1,3‐benzene dithiol (BDT) protected Ag 29 NCs studied. The Ni‐doped (NiAg 28 12 ) NCs, are synthesized using a co‐reduction method characterized electrospray ionization mass spectrometry (ESI MS), ion mobility (IMS), X‐ray photoelectron spectroscopy (XPS). Only single achieved despite changing precursor concentration. in exhibits enhanced thermal stability, electrocatalytic oxygen evolution reaction (OER) compared to parent NCs. Density functional theory (DFT) calculations predict geometry NiAg DFT also used study systematic effect metals such as Au, Cu, Pt into suggests that with Pt, d atomic orbitals contribute creating superatomic orbitals, which not seen other dopants or cluster. emission mechanism dominated by charge transfer from ligands core cluster regardless dopant.

Language: Английский

Citations

0