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

Published on Jul 22, 2020in Nature Communications12.121
· DOI :10.1038/S41467-020-17200-W
Xi-Yan Dong26
Estimated H-index: 26
(Zhengzhou University),
Yubing Si10
Estimated H-index: 10
(Zhengzhou University)
+ 6 AuthorsThomas C. W. Mak84
Estimated H-index: 84
(Zhengzhou University)
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. Incorporating dual fluorescence and phosphorescence into a single matrix is attractive for oxygen sensing, but material design is challenging. Here the authors achieve dual fluorescence-phosphorescence from a single linker chromophore in a silver chalcogenolate-cluster-based metal-organic framework.
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