Metal–organic frameworks (MOFs), which can be precisely tailored through inorganic metal nodes and their organic ligands, present a promising avenue for developing high-performance photocatalysts. Herein, two isostructural MOFs, UiO-68-NH₂ and UiO-68-BT, are synthesized using Zr₆O₄(OH)₄¹²⁺ clusters and linear dicarboxylic ligands. Adjusting the electron-withdrawing effect of the ligands from 2′-amino-[1,1′:4′,1″-terphenyl]-4,4″-dicarboxylic acid to 4,4′-(benzo[c][1,2,5]-thiadiazole-4,7-diyl)dibenzoic acid results in MOFs with varied optoelectronic properties. UiO-68-NH₂ shows no performance, whereas UiO-68-BT stands out for its exceptional photocatalytic performance in blue light-driven selective aerobic oxidation of benzylamine, achieving a conversion of 93% and selectivity of 99% in 45 min. Recycling tests further confirm the stability and reusability of UiO-68-BT, implying its potential as a durable photocatalyst. A variety of amines are converted swiftly with molecular oxygen, and the selective generation of imines is carried out by superoxide radical anion. This research highlights the benefits of modulating the electronic effect of organic ligands of MOF photocatalysts, opening a new avenue for aerobic oxidation reactions.

中文翻译：

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蓝光驱动苯并噻二唑金属有机骨架光催化选择性有氧氧化胺

金属有机框架（MOF）可以通过无机金属节点及其有机配体精确定制，为开发高性能光催化剂提供了一条有前途的途径。在此，使用Zr ₆ O ₄ (OH) ₄ ¹²⁺簇和线性二羧酸配体合成了两种同构MOF，UiO-68-NH ₂和UiO-68-BT。调整配体的吸电子效应从2'-氨基-[1,1':4',1"-三联苯]-4,4"-二羧酸到4,4'-(苯并[ c ][1 ,2,5]-噻二唑-4,7-二基)二苯甲酸导致MOF具有不同的光电特性。 UiO-68-NH ₂没有表现出任何性能，而UiO-68-BT在蓝光驱动的苯甲胺选择性有氧氧化中具有出色的光催化性能，在45分钟内实现了93%的转化率和99%的选择性。回收测试进一步证实了 UiO-68-BT 的稳定性和可重复使用性，这意味着其作为耐用光催化剂的潜力。多种胺与分子氧迅速转化，并通过超氧自由基阴离子选择性生成亚胺。这项研究强调了调节 MOF 光催化剂有机配体电子效应的好处，为有氧氧化反应开辟了新途径。