Robust Zn(II)-MOFs Built from Triphenylamine and Thiazolo[5,4- d ]thiazole Motifs for Photopromoted CO 2 Cycloaddition under Mild Conditions

作者：Chang‐Zheng Tu, Chixian He, Xiaoli Yan, Jian‐Jun Liu, Yuting Yang, Feixiang Cheng, Feng Luo · 发表于：Inorganic Chemistry · 年份：2025 · DOI：10.1021/acs.inorgchem.5c03203 · 被引用次数：8 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Carbon dioxide utilization in catalysis、Advanced Photocatalysis Techniques

The immobilization of photoresponsive motifs in metal–organic frameworks (MOFs) through a mixed-ligand strategy may provide more possibilities for optimizing functions such as catalysis, adsorption, and others. In this work, a novel complex {[Zn 2 (tcppda)(DPTzTz) 2 ]·3DMF} (MOF- 1 ) is obtained by assembling photoactive ligands 2,5-di(pyridin-4-yl)thiazolo[5,4- d ]thiazole (DPTzTz) and N, N, N ′, N ′-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine (H 4 tcppda) under solvothermal conditions. MOF- 1 possesses a 2-fold interpenetrated pillar-layered framework with open channels. The channel walls are decorated with high-density Lewis acidic Zn(II) centers and photoactive Lewis basic groups. The title MOF exhibits excellent thermal and chemical stability. The activated sample (MOF- 1a ) with permanent porosity exhibits photopromoted catalytic activity in the cycloaddition of CO 2 with epoxides under mild conditions. A reaction mechanism involving photogenerated electrons and holes is proposed to explain this enhancement. Furthermore, MOF- 1a retains its structural integrity and catalytic performance over five consecutive recycling runs. This work establishes that the photoactive structural motif is critical for driving CO 2 cycloaddition under ambient-relevant conditions.