Ligand engineering to achieve enhanced ratiometric oxygen sensing in a silver cluster-based metal-organic framework.
basic_science · Level V
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- Record sourced from PubMed, PMID 32699338.
- Also identified by DOI 10.1038/s41467-020-17200-w and PMC identifier 7376137.
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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 -NH<sub>2</sub> groups on the linkers of a silver-chalcogenolate-cluster-based metal-organic framework (Ag<sub>12</sub>bpy-NH<sub>2</sub>) 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. Ag<sub>12</sub>bpy-NH<sub>2</sub> 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.