合肥工业大学朱元元团队报道了二芳基二氢吩嗪基多孔有机聚合物增强可见光驱动有机转化的协同催化作用。相关研究成果于2023年8月24日发表在国际顶尖学术期刊《德国应用化学》。

多孔有机聚合物（POPs）是一类新型的多孔材料，由具有不同几何形状和拓扑结构的各种有机单体聚合而成。有机构建块的分子可调性能够结合用于光催化有机转化的功能单元。

该文中，研究人员报道了通过乙烯基官能化的二芳基二氢吩嗪（DAHP）单体（POP1）的均聚和乙烯基官能的DAHP和2，2'-联吡啶单体（POP 2）的共聚合合成两种基于POP的光催化剂。持久性有机污染物中DADHP单元的荧光寿命显著增加，与均匀对照相比，光催化性能增强。POP1在催化可见光驱动的C-N键形成交叉偶联反应方面非常有效。在与Ni²⁺离子配位后，由于POP框架内的限制效应，POP2-Ni在光催化循环和Ni催化循环之间表现出强烈的协同作用，导致能量、电子和有机自由基转移的高效率。

POP2-Ni在催化二芳基膦氧化物和芳基碘化物之间的C-P键形成反应方面表现出优异的活性。在C-N和C-P交叉偶联反应中，它们的光催化活性提高了30倍以上。这些POP催化剂很容易通过离心分离回收，并在六个催化循环中重复使用而不损失活性。因此，基于光敏剂的持久性有机污染物为多相光催化有机转化提供了一个很有前途的平台。

附：英文原文

Title: Diaryl Dihydrophenazine-Based Porous Organic Polymers Enhance Synergistic Catalysis in Visible-Light-Driven Organic Transformations

Author: Yan Cheng, Yan-Xiang Li, Chun-Hua Liu, Yuan-Yuan Zhu, Wenbin Lin

Issue&Volume: 2023-08-24

Abstract: Porous organic polymers (POPs) have emerged as a novel class of porous materials that are synthesized by the polymerization of various organic monomers with different geometries and topologies. The molecular tunability of organic building blocks allows the incorporation of functional units for photocatalytic organic transformations. Here, we report the synthesis of two POP-based photocatalysts via homo-polymerization of vinyl-functionalized diaryl dihydrophenazine (DADHP) monomer (POP1) and co-polymerization of vinyl-functionalized DADHP and 2,2’-bipyridine monomers (POP2). The fluorescence lifetimes of DADHP units in the POPs significantly increased, resulting in enhanced photocatalytic performances over homogeneous controls. POP1 is highly effective in catalysing visible-light-driven C-N bond forming cross-coupling reactions. Upon coordination with Ni2+ ions, POP2-Ni shows strong synergy between photocatalytic and Ni catalytic cycles due to the confinement effect within the POP framework, leading to high efficiency in energy, electron, and organic radical transfer. POP2-Ni displays excellent activity in catalysing C-P bond forming reactions between diarylphosphine oxides and aryl iodides. They increased the photocatalytic activities by more than 30-fold in C-N and C-P cross-coupling reactions. These POP catalysts were readily recovered via centrifugal separation and reused in six catalytic cycles without loss of activities. Thus, photosensitizer-based POPs provide a promising platform for heterogeneous photocatalytic organic transformations.

DOI: 10.1002/anie.202310470

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202310470