Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal–organic framework

• Published in: Nature chemistry Vol. 9; no. 7; pp. 689 - 697
• Main Authors: Huang, Ren-Wu, Wei, Yong-Sheng, Dong, Xi-Yan, Wu, Xiao-Hui, Du, Chen-Xia, Zang, Shuang-Quan, Mak, Thomas C. W.
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.07.2017; Nature Publishing Group
• Subjects: 639/638/541/961; 639/638/911; Analytical Chemistry; Biochemistry; Chemistry; Chemistry/Food Science; Clusters; Energy harvesting; Fluorescence; Grafting; Inorganic Chemistry; Ligands; Luminescence; Metal-organic frameworks; Metals; Optoelectronics; Organic Chemistry; Organic compounds; Physical Chemistry; Separation; Silver; Single crystals; Solar energy; Stability; Switching; Temperature effects; VOCs; Volatile organic compounds; X-ray diffraction
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.2718

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. The properties of discrete species can sometimes be improved by fixing them into extended materials. This strategy has now been applied to silver( I ) chalcogenide/chalcogenolate clusters, resulting in a metal–organic framework with enhanced stability and fluorescent sensing capabilities. Crystallographic analysis allows precise structural determination of guest binding, which is responsible for both emission turn-off and multicoloured turn-on.