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The Effect of Linker-to-Metal Energy Transfer on the Photooxidation Performance of an Isostructural Series of Pyrene-Based Rare-Earth Metal-Organic Frameworks

Authors: Quezada-Novoa VTiti HMVillanueva FYWilson MWBHowarth AJ


Affiliations

1 Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. W., Montreal, Quebec, H4B 1R6, Canada.
2 Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
3 Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.

Description

The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4 TBAPy) along with rare-earth (RE) ions is used for the synthesis of 9 isostructures of a metal-organic framework (MOF) with shp topology, named RE-CU-10 (RE = Y(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III)). The synthesis of each RE-CU-10 analogue requires different reaction conditions to achieve phase pure products. Single crystal X-ray diffraction indicates the presence of a RE9 -cluster in Y- to Tm-CU-10, while a RE11 -cluster is observed for Yb- and Lu-CU-10. The photooxidation performance of RE-CU-10 analogues is evaluated, observing competition between linker-to-metal energy transfer versus the generation of singlet oxygen. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide, with half-lives ranging from 4.0 to 5.8 min, some of the fastest reported to date using UV-irradiation and < 1 mol% catalyst, in methanol under O2 saturation.


Keywords: 2-chloroethyl ethyl sulfideligand-to-metal energy transfermetal-organic frameworksphotooxidationpyrenerare-earth metalssinglet oxygen


Links

PubMed: https://pubmed.ncbi.nlm.nih.gov/37116124/

DOI: 10.1002/smll.202302173