Visible to NIR‐II Photoluminescence of Atomically Precise Gold Nanoclusters

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(8)

Published: Nov. 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.

Language: Английский

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Triplet–triplet annihilation photon upconversion-mediated photochemical reactions

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 238 - 255

Published: March 21, 2024

Language: Английский

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

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

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

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

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Triplet properties and intersystem crossing mechanism of PtAg28 nanocluster sensitizers achieving low threshold and efficient photon upconversion

Nanoscale, Journal Year: 2024, Volume and Issue: 16(6), P. 3053 - 3060

Published: Jan. 1, 2024

The combination of the PtAg28 nanocluster sensitizer with a 9,10-diphenylanthracene emitter achieved low upconversion threshold 0.8 mW cm −2 at 532 nm excitation, along efficient under 1-sun conditions.

Language: Английский

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Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 511, P. 215868 - 215868

Published: April 22, 2024

Language: Английский

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Dissecting the Triplet-State Properties and Intersystem Crossing Mechanism of the Ligand-Protected Au₁₃ Superatom

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(49), P. 10967 - 10973

Published: Dec. 1, 2023

Icosahedral Au13 nanoclusters are among the most typical superatoms and of great interest as promising building blocks for nanocluster-assembled materials. Herein, key parameters involved in intersystem crossing (ISC) process [Au13(dppe)5Cl2]3+ (Au13; dppe = 1,2-bis(diphenylphosphino)ethane) were characterized. Quenching experiments using aromatic compounds revealed that T1 energy is 1.63 eV. An integrative interpretation our experimental results relevant literature uncovered important facts concerning superatom: ISC quantum yield unity due to ultrafast (∼1012 s-1), lowest absorption band includes contributions direct singlet-triplet transitions, there exists a large S1-T1 gap 0.73 To explain efficient ISC, El-Sayed rule was applied superatomic orbitals corresponding excited-state hole/electron distributions obtained from theoretical calculations. The strong spin-orbit coupling between S1 T2-T4 states offers reasonable explanation ISC.

Language: Английский

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Triplet Photosensitizers and Their Applications in Triplet–Triplet Annihilation Upconversion

ACS Applied Optical Materials, Journal Year: 2024, Volume and Issue: 2(9), P. 1803 - 1824

Published: March 22, 2024

Triplet–triplet annihilation upconversion (TTA-UC), which converts low-energy photons into high-energy photons, is based on linear photon absorption and shows high efficiency of luminescence with large anti-Stokes shifts; thus, it has vast applications in solar cells, photocatalysis, artificial photosynthesis, etc. Due to cascade photophysical processes intersystem crossing (ISC) triplet–triplet energy transfer (TTET) involved TTA-UC, the properties triplet photosensitizers (PSs) are critical for designing TTA-UC materials. For instance, strong light long excited-state lifetimes will make PSs abundant at state, makes consequent intermolecular TTET process more efficient, be improved as well. In this review, we include recent developments focus photochemistry these PSs, including molecular design rationales, ISC mechanisms electron-spin selectivity ISC. The methods increasing shifts heavy-atom-free discussed briefly. This information helpful future PSs.

Language: Английский

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Ligand Strategies for Regulating Atomically Precise CeO2 Nanoparticles: From Structure to Property

Molecules, Journal Year: 2025, Volume and Issue: 30(4), P. 846 - 846

Published: Feb. 12, 2025

The increasing interest in studying the structure-property relationships of ceria dioxide (CeO2) relies on fact that many factors are key to determining performance CeO2 materials. Despite great advances achieved, it remains a formidable challenge regulate nanoparticles at molecular level and gain in-depth insight into their relationships. What is reported here ligand strategy for regulating nanoparticles, terms not only shape, structure, surface composition, but also property. Atomically precise (also named nanoclusters) used as model system, which two Ce16 clusters gained by wet-chemical synthesis method. Featuring different carboxylate ligands surface, distinct formula, core geometry, photoelectric merits. This work reports first pair atomically nanoclusters with same number Ce atoms structures, highly desirable relationships, provides effect

Language: Английский

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Ligand Effects on Luminescence of Atomically Precise Gold Nanoclusters

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: 16(9), P. 2204 - 2211

Published: Feb. 21, 2025

Great efforts have been made to establish the structure-property relationships of ligand-protected metal nanoclusters. An alkynyl-protected gold nanocluster Au28(tBuC6H4C≡C)20 (Au28-C2) was synthesized and structurally characterized. It has an isostructural kernel a quite similar ligand shell its counterpart Au28(tBuC6H4S)20 (Au28-S), which provides valuable platform for studying effects on luminescence clusters. The emission intensity Au28-C2 in solution is ∼10-fold that Au28-S. only structural difference between these two clusters donor atom or group, i.e., C≡C versus S Temperature-dependent experiments indicate Au28 different thermodynamic behaviors radiative processes. study excited-state dynamics by transient absorption spectroscopy indicates larger triplet-state population than This work shows important properties nanoclusters, provide new perspectives designed synthesis functional

Language: Английский

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