Metal–organic frameworks (MOFs) with permanent porosity and multifunctional catalytic sites constructed by two or more organic ligands are regarded as effective heterogeneous catalysts to improve certain organic catalytic reactions. In this work, a pillared-layer Zn-MOF (MOF-LS10) was constructed by 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H₄TCPP) and 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole (DPTZTZ). After activation, MOF-LS10 has a permanent porosity and moderate CO₂ adsorption capacity. The introduction of thiazolo[5,4-d]thiazole (TZTZ), a photoactive unit, into the framework endows MOF-LS10 with excellent photocatalytic performance. MOF-LS10 can not only efficiently catalyze the formation of cyclic carbonates from CO₂ and epoxide substrates under mild conditions but also can photocatalyze benzylamine coupling at room temperature. In addition, we used another two ligands 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (H₄BTEB) and 1,4-di(pyridin-4-yl)benzene (DPB) to synthesize MOF-LS11 (constructed by BTEB^4– and DPTZTZ) and MOF-LS12 (constructed by TCPP^4– and DPB) in order to explore whether the pyrazine structural unit and the TZTZ structural unit synergistically catalyze the reaction. The electron paramagnetic resonance spectrum demonstrates that the superoxide radical (^·O₂^–), generated by electron transfer from the MOF excited by light to the oxidant, is the main active substance of oxidation. The design and synthesis of MOF-LS10 provide an effective synthetic strategy for the development of versatile heterogeneous catalysts for various organic reactions and a wide range of substrates.

中文翻译：

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噻唑并[5,4-d]噻唑基金属有机骨架催化CO2环加成和光催化苯甲胺偶联反应

由两个或多个有机配体构建的具有永久孔隙和多功能催化位点的金属有机框架（MOF）被认为是改善某些有机催化反应的有效多相催化剂。_{在这项工作中，由2,3,5,6-四(4-羧基苯基)吡嗪(H 4} TCPP)和2,5-二(pyridin-4-)构建了柱层Zn-MOF( MOF-LS10 )。基)噻唑并[5,4- d ]噻唑(DPTZTZ)。活化后，MOF-LS10具有永久的孔隙率和中等的CO ₂吸附能力。在骨架中引入光活性单元噻唑并[5,4- d ]噻唑（TZTZ）赋予MOF-LS10优异的光催化性能。MOF-LS10不仅可以在温和条件下有效催化CO ₂和环氧化物底物形成环状碳酸酯，而且可以在室温下光催化苯甲胺偶联。此外，我们还使用另外两个配体1,2,4,5-四(4-羧基苯基)苯(H ₄ BTEB)和1,4-二(吡啶-4-基)苯(DPB)合成了MOF-LS11 （由BTEB ^4-和DPTZTZ构建）和MOF-LS12 （由TCPP ^4-和DPB构建），以探讨吡嗪结构单元和TZTZ结构单元是否协同催化该反应。电子顺磁共振谱表明，光激发的MOF向氧化剂电子转移产生的超氧自由基( ^· O ₂ ^– )是氧化的主要活性物质。MOF-LS10的设计和合成为开发用于各种有机反应和各种底物的多功能多相催化剂提供了有效的合成策略。