Abstract：
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.
摘要：
四位接头，1,3,6,8-四（对苯甲酸）芘（H4TBAPy）与稀土（RE）离子一起用于合成具有shp拓扑的金属有机骨架（MOF）的9个同构结构，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相纯产物。单晶X射线衍射表明在Y-Tm-CU-10中存在RE9-簇,而对于Yb-和Lu-CU-10观察到RE11-簇。评估了RE-CU-10类似物的光氧化性能，观察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对芥子气模拟物2-氯乙基乙基硫醚进行解毒，半衰期从4.0到5.8分钟，迄今为止报道的一些最快的使用紫外线照射和<1摩尔%的催化剂，在甲醇中O2饱和。
