Perylene diimide (PDI) with its unique photoactive properties can be employed as an effective building block for synthesizing vigorous metal–organic frameworks (MOFs) and photocatalytic performance can be anticipated. Specifically, we introduce the fabrication of a zirconium-based MOF, Zr-PDI-Me, which is deliberately constructed using PDI units via a solvothermal process. The resulting Zr-PDI-Me exhibits a double interpenetrated topological structure and boasts a considerable specific surface area of up to 634 m² g⁻¹. Furthermore, its photoelectric response is satisfactory as evidenced by electrochemical characterization. Consequently, Zr-PDI-Me has served as a photocatalyst to selectively oxidize sulfides, demonstrating its excellent versatility. Importantly, it retains initial catalytic activity even after 5 cycles. Studies on the mechanism revealed that both superoxide radicals (O₂˙⁻) and singlet oxygen (¹O₂) promote the selective oxidation process to produce sulfoxides over Zr-PDI-Me. This work underscores the potential of incorporating photoresponsive organic functional groups into MOFs to create photoactive heterogeneous catalysts.

中文翻译：

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一种基于苝二酰亚胺的锆金属-有机框架，用于蓝光驱动的硫化物选择性氧化


苝二亚胺 （PDI） 具有独特的光活性特性，可以用作合成强力金属有机框架 （MOF） 的有效构建单元，并且可以预期光催化性能。具体来说，我们介绍了锆基 MOF Zr-PDI-Me 的制造，它是使用 PDI 单元通过溶剂热工艺特意构建的。所得的 Zr-PDI-Me 表现出双互穿拓扑结构，并拥有高达 634 m^{2 g-1} 的相当大的比表面积。此外，电化学表征证明其光电响应令人满意。因此，Zr-PDI-Me 已作为光催化剂选择性氧化硫化物，展示了其出色的多功能性。重要的是，即使在 5 次循环后，它仍能保持初始催化活性。对机制的研究表明，超氧自由基 （O₂ ̇⁻） 和单线态氧 （¹O₂） 都促进选择性氧化过程，在 Zr-PDI-Me 上产生亚砜。这项工作强调了将光响应有机官能团掺入 MOF 中以产生光活性非均相催化剂的潜力。