Quezada-Novoa Victor, Titi Hatem M, Villanueva Francisco Yarur, Wilson Mark W B, Howarth Ashlee J
Department of Chemistry and Biochemistry, Concordia University, 7141 Sherbrooke St. W., Montreal, Quebec, H4B 1R6, Canada.
Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal, Quebec, H3A 0B8, Canada.
Small. 2023 Sep;19(36):e2302173. doi: 10.1002/smll.202302173. Epub 2023 Apr 28.
The tetratopic linker, 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H 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 RE -cluster in Y- to Tm-CU-10, while a RE -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 O saturation.
四齿连接体1,3,6,8-四（对苯甲酸）芘（H TBAPy）与稀土（RE）离子一起用于合成具有shp拓扑结构的金属有机框架（MOF）的9种同构体，命名为RE-CU-10（RE = Y(III)、Gd(III)、Tb(III)、Dy(III)、Ho(III)、Er(III)、Tm(III)、Yb(III)和Lu(III)）。每种RE-CU-10类似物的合成需要不同的反应条件以获得纯相产物。单晶X射线衍射表明在Y至Tm-CU-10中存在RE-簇，而在Yb-和Lu-CU-10中观察到RE-簇。对RE-CU-10类似物的光氧化性能进行了评估，观察到连接体到金属的能量转移与单线态氧的产生之间的竞争。产生的单线态氧用于解毒芥子气模拟物2-氯乙基乙基硫醚，半衰期为4.0至5.8分钟，这是迄今为止在甲醇中O饱和条件下使用紫外线照射和<1 mol%催化剂报道的一些最快的半衰期。
