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

Abstract

AbstractThe 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 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.