Citation: Zhang Wen-Qiang, Li Qiu-Yan, Yang Xinyu, Ma Zheng, Wang Huanhuan, Wang Xiao-Jun. Benzothiadiazole Conjugated Metalorganic Framework for Organic Aerobic Oxidation Reactions under Visible Light[J]. Acta Chimica Sinica, ;2017, 75(1): 80-85. doi: 10.6023/A16090496 shu

Benzothiadiazole Conjugated Metalorganic Framework for Organic Aerobic Oxidation Reactions under Visible Light

Zhang Wen-Qiang ^a ,
Li Qiu-Yan ^a,*,, ,
Yang Xinyu ^a ,
Ma Zheng ^a ,
Wang Huanhuan ^b ,
Wang Xiao-Jun ^a,*,,

a.
School of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou 221116
b.
Laboratory of Environmental Science and Technology, Xinjiang Technical Institute of Physics & Chemistry, Urumqi 830011

Corresponding author: Li Qiu-Yan, qyli@jsnu.edu.cn Wang Xiao-Jun, xjwang@jsnu.edu.cn
Received Date: 17 September 2016

Fund Project: National Natural Science Foundation of China 21302218National Natural Science Foundation of China 21302072

Figures(7)

In the past several years, visible light induced organic transformations via photoredox catalysis have attracted increasing attention from chemists, owing to their mild, environmentally benign and low cost characteristics. Photoredox catalysts including noble metal complexes as well as some organic dyes are often used to promote the transformations under visible light irradiation. However, most of the reactions were conducted in homogeneous system, which makes it difficult to recycle the catalysts for reuse. From a sustainable viewpoint, an ideal photocatalyst should be easily recoverable, reusable and free of precious metals. To this end, photoactive metal-organic frameworks (MOFs) demonstrate unique advantageous features working as novel heterogeneous photocatalytic systems, yet their utilization toward organic transformations promoted by visible light has been limited. Herein we designed and synthesized a benzothiadiazole functionalized TPDC ligand H₂1 (TPDC=terphenyl-4, 4''-dicarboxylic acid). Briefly, a Suzuki reaction of 4, 7-dibromo-2, 1, 3-benzothiadiazole with 4-(methoxycarbonyl) phenylboronic acid yielded methyl ester precursor, which was hydrolysed by KOH to get the ligand H₂1 in a high yield. Dimethyl-substituted TPDC H₂2, on account of its better solubility, was synthesized to replace the original TPDC for preparation of MOF UiO-68 framework. Due to the same length of the two ligands, the mix-and-match synthetic strategy was utilized to construct the benzothiadiazole functionalized UiO-68 topological framework (i.e. MOF UiO-68-S). UiO-68-S was synthesized by heating the mixture of ZrCl₄ and a combination of ligands H₂1 and H₂2 (1:1 molar ratio) in N, N'-dimethylformamide (DMF) using HAc as an additive at 100℃ for 2 days. Powder X-ray diffraction (XRD) was em-ployed to confirm its crystalline nature and isostructural with the parent UiO-68 framework. Nitrogen sorption experiment at 77 K revealed a typical type I reversible isotherm with Brunauer-Emmett-Teller (BET) surface area up to 1135 m²·g^-1, indicating its high porosity. Moreover, the MOF can serve as a highly active photocatalyst for visible light promoted aerobic oxidation reactions, including the selective oxygenation of sulfides and oxidative hydroxylation of arylboronic acids. In addition, UiO-68-S can be recycled at least 5 times without significant loss of catalytic activity and its framework is maintained following the catalytic reaction.
- photocatalysis,
- metal-organic framework,
- benzothiadiazole,
- aerobic oxidation,
- heterogeneous catalysis
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