Porous aromatic frameworks with precisely controllable conjugation lengths for visible light-driven photocatalytic selective C-H activation reactions
Porous aromatic frameworks with precisely controllable conjugation lengths for visible light-driven photocatalytic selective C-H activation reactions
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DOI：
10.1016/j.eurpolymj.2020.110060
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发表时间：
2020-10
影响因子：
6
通讯作者：
Niklas Huber;Kai A. I. Zhang
中科院分区：
文献类型：
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作者：
Niklas Huber;Kai A. I. Zhang
有机可见光活性多孔聚合物是一类新型的多相光催化剂，在许多重要的光氧化还原反应中具有重要的应用前景。迄今为止，鉴于大多数基于聚合物的光催化剂通常具有完全共轭的性质，精确控制能带结构并因此精确控制其在光催化反应中的氧化还原电位，同时保持高活性表面积是一个巨大的挑战。在这里，我们设计了一系列的多孔芳香族框架（PAF）与精确控制的共轭长度内的聚合物结构作为有效的无金属光催化剂。该聚合物表现出高达1070 m2/g的高固有表面积以及可调的光学和氧化还原性质，允许应用于由光生电子或空穴物种选择性驱动的C-H活化反应。此外，作为高价值化学转化的一个有吸引力的例子，活性药物成分丹曲林的形成在简单的一锅级联合成中被PAF成功催化。
Organic visible light-active porous polymers have been established as a novel promising class of heterogeneous photocatalysts for a variety of important photoredox reactions. To date, given the usually fully conjugated nature of most polymer-based photocatalysts, precise control of the energy band structure and thereby their redox potentials in photocatalytic reactions while retaining highly active surface area is a huge challenge. Here, we design a series of porous aromatic frameworks (PAFs) with precise control of the conjugation length within the polymer architecture as efficient metal-free photocatalysts. The polymers exhibit a high intrinsic surface areas of up to 1070 m2/g as well as tunable optical and redox properties that allow applications in C-H activation reactions driven selectively either by the photogenerated electron or hole species. Furthermore, as an attractive example for high-value chemical conversions, the formation of dantrolene, an active pharmaceutical ingredient, was successfully catalyzed by the PAFs in the simple one-pot cascade synthesis.