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

作　　者：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 

机构地区：[1]New Cornerstone Science Laboratory,State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,National and Local Joint Engineering Research Center of Preparation Technology of Nanomaterials,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,China [2]KAUST Catalysis Center(KCC),Division of Physical Sciences and Engineering,King Abdullah University of Science and Technology(KAUST),Thuwal,Saudi Arabia [3]Advanced Membranes and Porous Materials Center,Division of Physical Science and Engineering,King Abdullah University of Science and Technology(KAUST),Thuwal,Saudi Arabia [4]Department of Physics and Chemistry,Nanoscience Center,University of Jyväskylä,Jyväskylä,Finland [5]Department of Chemistry and Chemical Biology,Harvard University,Cambridge,Massachusetts,USA [6]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen,China

出　　处：《Aggregate》2024年第2期447-456,共10页聚集体（英文）

基　　金：National Natural Science Foundation of China,Grant/Award Numbers:92261207,21890752;NSFC Center for Single-Atom Catalysis,Grant/Award Number:22388102;New Cornerstone Science Foundation;King Abdullah University of Science and Technology;Academy of Finland,Grant/Award Numbers:292352,319208。

摘　　要：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,Au_(18)Ag_(26)(R1COO)_(12)(R_(2)C≡C)_(24)(μ_(4)-O)_(2)(μ_(3)-O)_(2)(Au_(18_Ag_(26),where R_(1)=CH_(3-),Ph-,CHOPh-or CF3Ph-;R_(2)=Phor 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 1.6μs at ambient temperature.Meanwhile,Au18Ag26 shows outstanding stability against oxygen quenching and ambient conditions.Atomic level analysis reveals the strongπ⋯πand C-H⋯πinteractions from the aromatic alkynyl ligands and the enhancement of metal-oxygen-metal interactions by centrally coordinated O^(2−).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 O^(2−)-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.

关 键 词：Au-Ag-oxo nanoclusters PHOTOLUMINESCENCE RADIOLUMINESCENCE TADF X-ray imaging 

分 类 号：O64[理学—物理化学]