Ligand engineering to achieve enhanced ratiometric oxygen sensing in a silver cluster-based metal-organic framework

Xi-Yan Dong, Yubing Si, Jin-Sen Yang, Chong Zhang, Zhen Han, Peng Luo, Zhao-Yang Wang, Shuang-Quan Zang () and Thomas C. W. Mak
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Xi-Yan Dong: Zhengzhou University
Yubing Si: Zhengzhou University
Jin-Sen Yang: Zhengzhou University
Chong Zhang: Zhengzhou University
Zhen Han: Zhengzhou University
Peng Luo: Zhengzhou University
Zhao-Yang Wang: Zhengzhou University
Shuang-Quan Zang: Zhengzhou University
Thomas C. W. Mak: Zhengzhou University

Nature Communications, 2020, vol. 11, issue 1, 1-9

Abstract: Abstract Ratiometric luminescent oxygen sensing based on dual fluorescence and phosphorescence emission in a single matrix is highly desirable, yet the designed synthesis remains challenging. Silver-chalcogenolate-cluster-based metal-organic frameworks that combine the advantages of silver clusters and metal-organic frameworks have displayed unique luminescent properties. Herein, we rationally introduce −NH2 groups on the linkers of a silver-chalcogenolate-cluster-based metal-organic framework (Ag12bpy-NH2) to tune the intersystem crossing, achieving a dual fluorescence-phosphorescence emission from the same linker chromophore. The blue fluorescence component has a 100-nm gap in wavelength and 8,500,000-fold difference in lifetime relative to a yellow phosphorescence component. Ag12bpy-NH2 quantifies oxygen during hypoxia with the limit of detection of as low as 0.1 ppm and 0.3 s response time, which is visualized by the naked eye. Our work shows that metal cluster-based MOFs have great potential in luminescent sensing, and the longer-lived charge-separated states could find more photofunctional applications in solar energy transformation and photocatalysis.

Date: 2020
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DOI: 10.1038/s41467-020-17200-w

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