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

Nature Chemistry volume 9, pages 689–697 (2017)Cite this article

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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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Figure 1: Synthesis and crystal structure of Ag12bpy and observation of its microporosity and stability by adsorption and PXRD.
Figure 2: Luminescent quenching response to O2.
Figure 3: Sites of guests in the cavity of Ag12bpy.
Figure 4: Vapochromic responses of Ag12bpy and logic gate.

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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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  1. Ren-Wu Huang and Yong-Sheng Wei: These authors contributed equally to this work

Authors and Affiliations

  1. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Ren-Wu Huang, Yong-Sheng Wei, Xi-Yan Dong, Xiao-Hui Wu, Chen-Xia Du, Shuang-Quan Zang & Thomas C. W. Mak

  2. Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China

    Thomas C. W. Mak

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Contributions

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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Correspondence to Shuang-Quan Zang.

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Supplementary information

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Supplementary information (PDF 13263 kb)

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Supplementary Movie 1 (MP4 945 kb)

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Supplementary Movie 2 (MP4 440 kb)

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Supplementary Movie 3 (MP4 659 kb)

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Supplementary Movie 4 (MP4 466 kb)

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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)

Supplementary information

Crystallographic data for compound Ag12bpy-100K (CIF 253 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·O2-290K (CIF 291 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·O2-100K (CIF 256 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·EtOH (CIF 333 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Chloroform (CIF 244 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Acetonitrile (CIF 894 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Acetone (CIF 1014 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Cyclohexane (CIF 273 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Dioxane (CIF 1180 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Benzene (CIF 942 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Toluene (CIF 1148 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Fluorobenzene (CIF 2425 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Chlorobenzene (CIF 1024 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Bromobenzene (CIF 294 kb)

Supplementary information

Crystallographic data for compound Ag12bpy·Iodobenzene (CIF 533 kb)

Supplementary information

Crystallographic data for compound Ag12bpy· o -Xylene (CIF 558 kb)

Supplementary information

Crystallographic data for compound Ag12bpy· m -Xylene (CIF 797 kb)

Supplementary information

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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