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

30 January 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The rectangular tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H4TBAPy) 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 high quality phase pure products. Single crystal X-ray diffraction indicates the presence of a RE9-cluster in Y- to Tm-CU-10, while a unique RE11-cluster is observed for Yb- and Lu-CU-10. The photooxi-dation performance of the reported RE-CU-10 analogues is evaluated, giving insight into the competitive process of ligand-to-metal energy transfer versus the generation of singlet oxygen by RE-CU-10. The singlet oxygen produced is used to detoxify a mustard gas simulant 2-chloroethylethyl sulfide (2-CEES) to 2-chloroethyl ethyl sulfoxide (2-CEESO), 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.


metal-organic frameworks
rare-earth MOFs
rare-earth clusters
lanthanide MOFs
singlet oxygen
mustard gas

Supplementary materials

Supporting Information
Experimental details, TGA, SEM images, GC and ICP data, NMR, UV-Vis, photoluminescence, SCXRD


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.