Abstract
Silver(i) chalcogenide/chalcogenolate clusters are promising photofunctional materials for sensing, optoelectronics and solar energy harvesting applications. However, their instability and poor room-temperature luminescent quantum yields have hampered more extensive study. Here, we graft such clusters to adaptable bridging ligands, enabling their interconnection and the formation of rigid metal–organic frameworks. By controlling the spatial separation and orientation of the clusters, they then exhibit enhanced stability (over one year) and quantum yield (12.1%). Ultrafast dual-function fluorescence switching (<1 s) is also achieved, with turn-off triggered by O2 and multicoloured turn-on by volatile organic compounds. Single-crystal X-ray diffraction of the inclusion materials, obtained by single-crystal-to-single-crystal transformation, enables precise determination of the position of the small molecules within the framework, elucidating the switching mechanism. The work enriches the cluster-based metal–organic framework portfolio, bridges the gap between silver chalcogenide/chalcogenolate clusters and metal–organic frameworks, and provides a foundation for further development of functional silver-cluster-based materials.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (grants nos 21671175, 21371153 and 21371154), the Program for Science & Technology Innovation Talents in Universities of Henan Province (no. 164100510005) and Zhengzhou University. The authors thank Y.-Y. Zhu and D.-H. Wei for discussions on DFT calculations. The authors also thank J.-P. Zhang (Sun Yat-Sen University, Guangzhou, China) for discussions and help, and F. Pan (Central China Normal University, Wuhan, China) for his direction and help with crystallographic resolution.
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S.-Q.Z. conceived and designed the experiments. R.-W.H. and Y.-S.W. conducted the synthesis. R.-W.H. and X.-H.W. performed SCXRD measurements and crystal structure analyses. R.-W.H., X.-H.W., X.-Y.D., C.-X.D. and S.-Q.Z. performed physical measurements. S.-Q.Z., R.-W.H. and T.C.W.M. co-wrote the manuscript.
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Crystallographic data for compound Ag12 (CIF 2082 kb)
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Crystallographic data for compound Ag12bpy-290K (CIF 290 kb)
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Crystallographic data for compound Ag12bpy-100K (CIF 253 kb)
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Crystallographic data for compound Ag12bpy·O2-290K (CIF 291 kb)
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Crystallographic data for compound Ag12bpy·O2-100K (CIF 256 kb)
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Crystallographic data for compound Ag12bpy·EtOH (CIF 333 kb)
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Crystallographic data for compound Ag12bpy·Chloroform (CIF 244 kb)
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Crystallographic data for compound Ag12bpy·Acetonitrile (CIF 894 kb)
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Crystallographic data for compound Ag12bpy·Acetone (CIF 1014 kb)
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Crystallographic data for compound Ag12bpy·Cyclohexane (CIF 273 kb)
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Crystallographic data for compound Ag12bpy·Dioxane (CIF 1180 kb)
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Crystallographic data for compound Ag12bpy·Benzene (CIF 942 kb)
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Crystallographic data for compound Ag12bpy·Toluene (CIF 1148 kb)
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Crystallographic data for compound Ag12bpy·Fluorobenzene (CIF 2425 kb)
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Crystallographic data for compound Ag12bpy·Chlorobenzene (CIF 1024 kb)
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Crystallographic data for compound Ag12bpy·Bromobenzene (CIF 294 kb)
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Crystallographic data for compound Ag12bpy·Iodobenzene (CIF 533 kb)
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Crystallographic data for compound Ag12bpy· o -Xylene (CIF 558 kb)
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Crystallographic data for compound Ag12bpy· m -Xylene (CIF 797 kb)
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Crystallographic data for compound Ag12bpy· p -Xylene (CIF 993 kb)
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Huang, RW., Wei, YS., Dong, XY. et al. Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal–organic framework. Nature Chem 9, 689–697 (2017). https://doi.org/10.1038/nchem.2718
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DOI: https://doi.org/10.1038/nchem.2718
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