Authors: Quezada-Novoa V, Titi HM, Villanueva FY, Wilson MWB, Howarth AJ
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 sulfide; ligand-to-metal energy transfer; metal-organic frameworks; photooxidation; pyrene; rare-earth metals; singlet oxygen;
PubMed: https://pubmed.ncbi.nlm.nih.gov/37116124/