Intramolecular Aggregation‐Induced Surface Coupling of Metal Nanoclusters: Structure Elucidation and Photoluminescence Manipulation DOI Creative Commons
Jian Zhu, Rui Zhao,

Honglei Shen

et al.

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

Published: Dec. 10, 2024

ABSTRACT The restriction of the molecular motion has been extensively exploited in tailoring photoluminescence (PL) metal nanoclusters, while activation such a at level remains highly challenging. In this work, two‐step strategy, that is, surface activating and coupling, was proposed to induce nanoclusters level, corresponding underwent emission appearance enhancement. peripheral phosphine ligand functionalization alkali cation introduction gave rise series structural‐correlated M + ‐incorporated Cu 14 (M = Li, Na, K, Rb, Cs) with surface‐aggregation characteristic, among which K ‐participating nanocluster displayed strongest fluorescence intensity both solution crystal states. Atomic‐level structure–property correlations were investigated rationalize PL comparisons. Overall, work offers new perspective for regulating via restricting their motions, hopefully providing insight into fabrication emissive cluster‐based nanomaterials.

Language: Английский

Low Optical Loss and Bent Waveguides: Crystals of a One-Dimensional Pt1Ag14 Nanocluster DOI

Chuanjun Zhou,

Wei Huang, Kaiyang Kuang

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

Photoluminescent nanoclusters are promising materials for optical waveguides. However, their photon transmission under mechanical stress is very challenging. Here, we report an low-loss metallic nanocluster crystal, [Pt1Ag14(DPPP)6Cl4](SbF6)2 (DPPP = 1,3-bis(diphenylphosphino) propane), which exhibits stable performance with loss coefficient of 7.15 × 10–4 dB·μm–1─lower than most reported inorganic, organic, and hybrid materials. The Pt1Ag14 crystals maintain excellent stability deformation, difference only 0.15 10–3 dB·μm–1 before after stress. Reasonable molecular design endows robust flexibility, resulting in bending radius being smaller that similar structures. Structural analysis has shown multiple π···π, C–H···π, C–H···F intra- intermolecular interactions originating from the ligands between counterions ensure crystal Metallic low flexibility generated by rational offer candidates fields active waveguides flexible electronic

Language: Английский

Citations

1
Heteroatom number-dependent cluster frameworks in structurally comparable Pd–Au nanoclusters DOI

Ziwei Fu,

Li Chen, Ye Tian

et al.

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

Published: Jan. 1, 2025

This work achieved the manipulation of Pd dopant numbers in cluster framework based on two structurally comparable x Au 12 ( = 1, 2) nanoclusters.

Language: Английский

Citations

0
Tightly bonded excitons in chiral metal clusters for luminescent brilliance DOI Creative Commons
Zhen Han,

Chunbo Duan,

Xi‐Yan Dong

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 21, 2025

Chiral metal clusters have promise for circularly polarized luminescent materials; however, the absence of a unified understanding emission mechanism causes challenges in designing high-efficiency lighting materials based on these clusters. These primarily arise from their vast structural variability and intricate emissive states. In this study, we show crucial roles exciton binding energy electron‒phonon interactions achieving phosphorescence. Through Cu doping Au4 changing ligand substituents, increase energies reduce interactions; results maximum 1.3-fold radiative recombination rate, 241.1-fold decrease nonradiative ultimately phosphorescence quantum yield over 96% luminescence cluster crystals. A solution-processed light-emitting diode prototype exhibits an external efficiency 15.51% green dissymmetry factor |gEL| 7.6 × 10−3. Our findings highlight significance with optimized enhanced optoelectronic performance, including optoelectronics. but limits design. Here, authors high

Language: Английский

Citations

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

Xue Wang,

Zhou Huang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 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.

Language: Английский

Citations

0
Highly Efficient Upconverted Fluorescence from Coulombically Assembled Ion Pair DOI Creative Commons

Ji Hye Baek,

Dayoon Song,

Gyurim Park

et al.

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Abstract An ion pair consisting of a dicationic Os(II) complex and two monoanionic fluorophores is designed prepared. The exhibited strong upconverted (UC) greenish blue fluorescence emission upon photoexcitation the entity at wavelength 785 nm, with high quantum yield 13% (its theoretical limit 50%) low threshold excitation intensity 5.9 mW cm −2 . This least an order magnitude smaller than those obtained for previous systems, demonstrating sensitivity system UC emission. notable improvements results over systems are attributed to diffusion‐free acceleration bimolecular processes, including triplet‐triplet energy transfer annihilation, within Coulombically bound containing photosensitizer fluorescent annihilators in 1:2 stoichiometry, which ideal annihilation‐based upconversion.

Language: Английский

Citations

0
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

3
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
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
Luminescent Metal Nanoclusters and Their Application in Bioimaging DOI
Wenwen Fei,

Sheng-Yan Tang,

Man‐Bo Li

et al.

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

Published: Jan. 1, 2024

This review focuses on the structure–property correlation and bioimaging application of luminescent metal nanoclusters, which feature atomically precise structures, diverse optical properties excellent biocompatibility.

Language: Английский

Citations

0
Size disproportionation among nanocluster transformations DOI Creative Commons
Zhu Chen, Luyao Lu, Fei Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Controllable transformation is a prerequisite to the in-depth understanding of structure evolution mechanisms and structure-property correlations at atomic level. Most cases direct directional nanocluster sizes,

Language: Английский

Citations

0