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
Affiliations
Peng Yuan
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
Hansong Zhang
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
Yang Zhou
Advanced Membranes and Porous Materials Center Division of Physical Science and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Tengyue He
Advanced Membranes and Porous Materials Center Division of Physical Science and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Sami Malola
Department of Physics and Chemistry Nanoscience Center University of Jyväskylä Jyväskylä Finland
Luis Gutiérrez‐Arzaluz
Advanced Membranes and Porous Materials Center Division of Physical Science and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Yingwei Li
Department of Chemistry and Chemical Biology Harvard University Cambridge Massachusetts USA
Guocheng Deng
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
Chunwei Dong
KAUST Catalysis Center (KCC) Division of Physical Sciences and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Renwu Huang
KAUST Catalysis Center (KCC) Division of Physical Sciences and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Xin Song
KAUST Catalysis Center (KCC) Division of Physical Sciences and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Boon K. Teo
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
Omar F. Mohammed
Advanced Membranes and Porous Materials Center Division of Physical Science and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Hannu Häkkinen
Department of Physics and Chemistry Nanoscience Center University of Jyväskylä Jyväskylä Finland
Osman. M. Bakr
KAUST Catalysis Center (KCC) Division of Physical Sciences and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal Saudi Arabia
Nanfeng Zheng
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
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.
