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

Nature Communications
Xi-Yan DongThomas C W Mak

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.

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Citations

Apr 16, 2021·Inorganic Chemistry·Kenta SasakiMasaaki Ohba
May 8, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Yanhui TaoZhi-Gang Ren
Jun 12, 2021·ACS Applied Materials & Interfaces·Yuanchao LvYong Sheng Zhao
Jun 29, 2021·Journal of the American Chemical Society·Guocheng DengNanfeng Zheng
Jul 30, 2021·Chemistry, an Asian Journal·Shivani SharmaSujit K Ghosh
Aug 18, 2021·Inorganic Chemistry·Yoshinobu KamakuraDaisuke Tanaka
Sep 28, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Ziyu TangSimon G Podkolzin
Oct 12, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Na-Na LiShuang-Quan Zang

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Methods Mentioned

BETA
X-ray
phosphorescence

Software Mentioned

RIJONX
ORCA
Multiwfn
GaussSum
CrysAlisPro
SHELXL
SHELXS
PLATON
OLEX2

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