Journal
NATURE CHEMISTRY
Volume 9, Issue 7, Pages 689-697Publisher
NATURE PUBLISHING GROUP
DOI: 10.1038/NCHEM.2718
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Funding
- National Natural Science Foundation of China [21671175, 21371153, 21371154]
- Program for Science & Technology Innovation Talents in Universities of Henan Province [164100510005]
- Zhengzhou University
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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 O-2 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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