Highly Efficient and Selective Photooxidation of Sulfur Mustard Simulant by a Triazolobenzothiadiazole-Moiety-Functionalized Metal–Organic Framework in Air

Abstract

A photoactive triazolobenzothiadiazole (TBTD)-conjugated terphenyldicarboxylate (TPDC) linker was introduced into a porous and robust UiO-68 isoreticular zirconium metal-organic framework (denoted as UiO-68-TBTD) by the de novo synthetic approach of mixed TPDC struts. Under blue-light-emitting-diode irradiation, UiO-68-TBTD can serve as a heterogeneous photocatalyst for the highly efficient and selective oxidation of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) to the corresponding much less toxic sulfoxide product, with a half-life of only 3 min in the open air atmosphere.

Implementing fluorescent MOFs as down-converting layers in hybrid light-emitting diodes

“…19 Previously, related linkers containing central benzothiadiazole units flanked by two benzoic acid rings have been used to prepare Zr MOFs with UiO-68 topologies to sense picric acid 24 and organic amines, 25 or to photocatalytically degrade mustard gas simulants. 26,27 A selenothiadiazole analogue has also been utilised to photocatalyse dehydrogenative cross-coupling reactions. 28 In all but one case, 25 a mixed-linker synthetic strategy was used to prepare the MOF, where the photoactive ligand was diluted within the solid with an unsubstituted terphenyl analogue.…”

Imine‐Based Covalent Organic Frameworks as Photocatalysts for Metal Free Oxidation Processes under Visible Light Conditions

“…Moreover, the overoxidation process to sulfone has been also described as a limitation to be overcome. However, although the use of materials in the sulfoxidation reactions has been explored, [14][15][16][17][18][19][20][21][22] several limitations have been frequently described, such as the use of high powered light energy (> 150 W), [14] materials decorated with toxic metals, [16] non-green solvents and moderate recyclability. [8][9][10][11][12][13] Therefore, an alternative oxidation for the use of peracids and peroxides is the application of gaseous reagents that allows the development of greener processes by reducing the waste from purification, because excess of gas can be easily removed from the reaction.…”

“…Although in most cases the use of oxygen for the oxidation of sulfides has been carried out with homogeneous systems, the use of heterogeneous materials, especially those containing porosity in their structure, seems one of the most logical approaches for the use of gases in catalysis. However, although the use of materials in the sulfoxidation reactions has been explored, [14][15][16][17][18][19][20][21][22] several limitations have been frequently described, such as the use of high powered light energy (> 150 W), [14] materials decorated with toxic metals, [16] non-green solvents and moderate recyclability. [16] Overcoming such drawbacks would be highly desirable in order to achieve a green process.…”

Catalytic Processes for the Neutralization of Sulfur Mustard

“…Farah and co-workersd eveloped heterogeneous catalysts for CWAd econtamination based on MOFs made of zirconium oxide clusters (Zr 6 O 8 )asnodes and different organic PS-bearing carboxylate groups as linkers. Ag reat variety of PS were used as linkers, for example, tetrabenzoateporphyrin, [119,120] tetrabenzoatepyrene, [121,122] tetrabenzoateperylene, [123] benzothiadiazole, and benzoselenodiazole [124,125] ,a nd as the interstitial component in the MOF channels, [6,6]-phenyl-C 61 -butyrate (PCB), [126] or different BODIPY derivatives [127] were used ( Figure 10). MOFs containing the Zr 6 O 8 cluster werep reviously shown to have limited hydrolytic activity towards CEES, [128] but under suitable light irradiation fast and selectivec onversion of CEES to the sulfoxide derivativew as obtained for all PS-containing MOFs.…”