A mesoporous metal-organic framework with photothermal properties, namely PCN-222, was solvothermally synthesized from meso-tetra(4-carboxyphenyl)porphyrin and zirconium chloride employing both benzoic acid (BA) and trifluoroacetic acid (TFA) as modifiers. The MOF material subsequently served as a porous support for a polyoxometalate (POM), H₃PW₁₂O₄₀, via a facile impregnation method which rendered a novel porous POM@PCN-222 composite. The solid was characterized by FT-IR, PXRD, SEM/EDX, TGA/DSC, ICP-OES, UV–Vis DRS, cyclic voltammetry (CV), and BET surface area. The one-pot synthesis of N-heterocycles (pyridine derivatives) was investigated utilizing the hybrid material via one-pot pseudo four-component reaction between aromatic aldehydes, methyl acetoacetate and ammonium acetate promoted under visible LED light irradiation in the presence of molecular oxygen as green oxidant. Products were selectively formed in good yields in the presence of the recyclable heterogeneous solid. Remarkably, POM@PCN-222 showed a superior performance for this procedure as compared to both unfunctionalized MOF and POM. The photosensitizer and photothermal properties of the porphyrin linkers combined with Lewis acidic sites derived from PW₁₂ and Zr₆-nodes were responsible for the observed excelling performance. To understand the mechanism, control investigations, electron paramagnetic resonance (EPR) analysis and FT-IR reaction monitoring were performed. The work discloses, for the first time, a simple and environmentally friendly approach for the direct production of pyridines via one-pot thermo-photocatalytic approach using a novel POM-modified MOF in the absence of any chemical additive.

以苯甲酸 (BA) 和三氟乙酸 (TFA) 作为改性剂，由内消旋四 (4-羧基苯基) 卟啉和氯化锆溶剂热合成具有光热性能的介孔金属有机骨架，即 PCN-222 。MOF 材料随后作为多金属氧酸盐 (POM)、H ₃ PW ₁₂ O ₄₀的多孔载体，通过一种简便的浸渍方法提供了一种新型的多孔 POM@PCN-222 复合材料。通过 FT-IR、PXRD、SEM/EDX、TGA/DSC、ICP-OES、UV-Vis DRS、循环伏安法 (CV) 和 BET 表面积表征固体。N的一锅合成在分子氧作为绿色氧化剂的存在下，在可见 LED 光照射下，通过芳香醛、乙酰乙酸甲酯和乙酸铵之间的一锅假四组分反应，利用杂化材料研究了杂环化合物（吡啶衍生物）。在可回收的多相固体存在下，以良好的收率选择性地形成产物。值得注意的是，与未功能化的 MOF 和 POM 相比，POM@PCN-222 在该过程中表现出优异的性能。卟啉接头与来自 PW ₁₂和 Zr _{6 的}路易斯酸性位点结合的光敏剂和光热性能-nodes 负责观察到的出色性能。为了了解其机制，进行了对照研究、电子顺磁共振 (EPR) 分析和 FT-IR 反应监测。该工作首次公开了一种简单且环保的方法，通过一锅热光催化方法使用新型 POM 修饰的 MOF 在没有任何化学添加剂的情况下直接生产吡啶。