Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters: From photoluminescence to radioluminescence

Peng Yuan; Hansong Zhang; Yang Zhou; Tengyue He; Sami Malola; Luis Gutiérrez-Arzaluz; Yingwei Li; Guocheng Deng; Chunwei Dong; Renwu Huang; Xin Song; Boon K. Teo; Omar F. Mohammed; Hannu Häkkinen; Osman M. Bakr; Nanfeng Zheng

doi:10.1002/agt2.475

Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters: From photoluminescence to radioluminescence

Peng Yuan^*, Hansong Zhang, Yang Zhou, Tengyue He, Sami Malola, Luis Gutiérrez-Arzaluz, Yingwei Li, Guocheng Deng, Chunwei Dong, Renwu Huang, Xin Song, Boon K. Teo, Omar F. Mohammed, Hannu Häkkinen^*, Osman M. Bakr^*, Nanfeng Zheng^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Thermally activated delayed fluorescence (TADF) materials have numerous applications in energy conversion and luminescent imaging. However, they are typically achieved as metal-organic complexes or pure organic molecules. Herein, we report the largest Au-Ag-oxo nanoclusters to date, Au₁₈Ag₂₆(R₁COO)₁₂(R₂C≡C)₂₄(μ₄-O)₂(μ₃-O)₂ (Au₁₈Ag₂₆, where R₁ = CH₃-, Ph-, CHOPh- or CF₃Ph-; R₂ = Ph- or FPh-). These nanoclusters exhibit exceptional TADF properties, including a small S₁-T₁ energy gap of 55.5 meV, a high absolute photoluminescence quantum yield of 86.7%, and a microseconds TADF decay time of 1.6 μs at ambient temperature. Meanwhile, Au₁₈Ag₂₆ shows outstanding stability against oxygen quenching and ambient conditions. Atomic level analysis reveals the strong π⋯π and C-H⋯π interactions from the aromatic alkynyl ligands and the enhancement of metal-oxygen-metal interactions by centrally coordinated O²⁻. Modeling of the electronic structure shows spatially separated highest occupied molecular orbital and lowest unoccupied molecular orbital, which promote charge transfer from the ligand shell, predominantly carboxylate ligands, to O²⁻-embedded metal core. Furthermore, TADF Au-Ag-oxo nanoclusters exhibit promising radioluminescence properties, which we demonstrate for X-ray imaging. Our work paves the way for the design of TADF materials based on large metal nanoclusters for light-emission and radioluminescence applications.

Original language	English (US)
Article number	e475
Journal	Aggregate
Volume	5
Issue number	2
DOIs	https://doi.org/10.1002/agt2.475
State	Published - Apr 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Aggregate published by South China University of Technology; AIE Institute and John Wiley & Sons Australia, Ltd.

Keywords

Au-Ag-oxo nanoclusters
photoluminescence
radioluminescence
TADF
X-ray imaging

ASJC Scopus subject areas

Chemistry (miscellaneous)
Materials Science (miscellaneous)
Materials Chemistry
Molecular Biology

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10.1002/agt2.475

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Yuan, P., Zhang, H., Zhou, Y., He, T., Malola, S., Gutiérrez-Arzaluz, L., Li, Y., Deng, G., Dong, C., Huang, R., Song, X., Teo, B. K., Mohammed, O. F., Häkkinen, H., Bakr, O. M., & Zheng, N. (2024). Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters: From photoluminescence to radioluminescence. Aggregate, 5(2), Article e475. https://doi.org/10.1002/agt2.475

@article{f48a3fd1d142411b8f38805a55c0bce1,

title = "Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters: From photoluminescence to radioluminescence",

abstract = "Thermally activated delayed fluorescence (TADF) materials have numerous applications in energy conversion and luminescent imaging. However, they are typically achieved as metal-organic complexes or pure organic molecules. Herein, we report the largest Au-Ag-oxo nanoclusters to date, Au18Ag26(R1COO)12(R2C≡C)24(μ4-O)2(μ3-O)2 (Au18Ag26, where R1 = CH3-, Ph-, CHOPh- or CF3Ph-; R2 = Ph- or FPh-). These nanoclusters exhibit exceptional TADF properties, including a small S1-T1 energy gap of 55.5 meV, a high absolute photoluminescence quantum yield of 86.7%, and a microseconds TADF decay time of 1.6 μs at ambient temperature. Meanwhile, Au18Ag26 shows outstanding stability against oxygen quenching and ambient conditions. Atomic level analysis reveals the strong π⋯π and C-H⋯π interactions from the aromatic alkynyl ligands and the enhancement of metal-oxygen-metal interactions by centrally coordinated O2−. Modeling of the electronic structure shows spatially separated highest occupied molecular orbital and lowest unoccupied molecular orbital, which promote charge transfer from the ligand shell, predominantly carboxylate ligands, to O2−-embedded metal core. Furthermore, TADF Au-Ag-oxo nanoclusters exhibit promising radioluminescence properties, which we demonstrate for X-ray imaging. Our work paves the way for the design of TADF materials based on large metal nanoclusters for light-emission and radioluminescence applications.",

keywords = "Au-Ag-oxo nanoclusters, photoluminescence, radioluminescence, TADF, X-ray imaging",

author = "Peng Yuan and Hansong Zhang and Yang Zhou and Tengyue He and Sami Malola and Luis Guti{\'e}rrez-Arzaluz and Yingwei Li and Guocheng Deng and Chunwei Dong and Renwu Huang and Xin Song and Teo, {Boon K.} and Mohammed, {Omar F.} and Hannu H{\"a}kkinen and Bakr, {Osman M.} and Nanfeng Zheng",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Aggregate published by South China University of Technology; AIE Institute and John Wiley & Sons Australia, Ltd.",

year = "2024",

month = apr,

doi = "10.1002/agt2.475",

language = "English (US)",

volume = "5",

journal = "Aggregate",

issn = "2766-8541",

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TY - JOUR

T1 - Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters

T2 - From photoluminescence to radioluminescence

AU - Yuan, Peng

AU - Zhang, Hansong

AU - Zhou, Yang

AU - He, Tengyue

AU - Malola, Sami

AU - Gutiérrez-Arzaluz, Luis

AU - Li, Yingwei

AU - Deng, Guocheng

AU - Dong, Chunwei

AU - Huang, Renwu

AU - Song, Xin

AU - Teo, Boon K.

AU - Mohammed, Omar F.

AU - Häkkinen, Hannu

AU - Bakr, Osman M.

AU - Zheng, Nanfeng

PY - 2024/4

Y1 - 2024/4

N2 - Thermally activated delayed fluorescence (TADF) materials have numerous applications in energy conversion and luminescent imaging. However, they are typically achieved as metal-organic complexes or pure organic molecules. Herein, we report the largest Au-Ag-oxo nanoclusters to date, Au18Ag26(R1COO)12(R2C≡C)24(μ4-O)2(μ3-O)2 (Au18Ag26, where R1 = CH3-, Ph-, CHOPh- or CF3Ph-; R2 = Ph- or FPh-). These nanoclusters exhibit exceptional TADF properties, including a small S1-T1 energy gap of 55.5 meV, a high absolute photoluminescence quantum yield of 86.7%, and a microseconds TADF decay time of 1.6 μs at ambient temperature. Meanwhile, Au18Ag26 shows outstanding stability against oxygen quenching and ambient conditions. Atomic level analysis reveals the strong π⋯π and C-H⋯π interactions from the aromatic alkynyl ligands and the enhancement of metal-oxygen-metal interactions by centrally coordinated O2−. Modeling of the electronic structure shows spatially separated highest occupied molecular orbital and lowest unoccupied molecular orbital, which promote charge transfer from the ligand shell, predominantly carboxylate ligands, to O2−-embedded metal core. Furthermore, TADF Au-Ag-oxo nanoclusters exhibit promising radioluminescence properties, which we demonstrate for X-ray imaging. Our work paves the way for the design of TADF materials based on large metal nanoclusters for light-emission and radioluminescence applications.

AB - Thermally activated delayed fluorescence (TADF) materials have numerous applications in energy conversion and luminescent imaging. However, they are typically achieved as metal-organic complexes or pure organic molecules. Herein, we report the largest Au-Ag-oxo nanoclusters to date, Au18Ag26(R1COO)12(R2C≡C)24(μ4-O)2(μ3-O)2 (Au18Ag26, where R1 = CH3-, Ph-, CHOPh- or CF3Ph-; R2 = Ph- or FPh-). These nanoclusters exhibit exceptional TADF properties, including a small S1-T1 energy gap of 55.5 meV, a high absolute photoluminescence quantum yield of 86.7%, and a microseconds TADF decay time of 1.6 μs at ambient temperature. Meanwhile, Au18Ag26 shows outstanding stability against oxygen quenching and ambient conditions. Atomic level analysis reveals the strong π⋯π and C-H⋯π interactions from the aromatic alkynyl ligands and the enhancement of metal-oxygen-metal interactions by centrally coordinated O2−. Modeling of the electronic structure shows spatially separated highest occupied molecular orbital and lowest unoccupied molecular orbital, which promote charge transfer from the ligand shell, predominantly carboxylate ligands, to O2−-embedded metal core. Furthermore, TADF Au-Ag-oxo nanoclusters exhibit promising radioluminescence properties, which we demonstrate for X-ray imaging. Our work paves the way for the design of TADF materials based on large metal nanoclusters for light-emission and radioluminescence applications.

KW - Au-Ag-oxo nanoclusters

KW - photoluminescence

KW - radioluminescence

KW - TADF

KW - X-ray imaging

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U2 - 10.1002/agt2.475

DO - 10.1002/agt2.475

M3 - Article

AN - SCOPUS:85181258465

SN - 2766-8541

VL - 5

JO - Aggregate

JF - Aggregate

IS - 2

M1 - e475

ER -

Thermally activated delayed fluorescence Au-Ag-oxo nanoclusters: From photoluminescence to radioluminescence

Abstract

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