Mazzanti Stefano, Schritt Clara, Ten Brummelhuis Katharina, Antonietti Markus, Savateev Aleksandr
Max-Planck Institute of Colloids and Interfaces, Department of Colloid Chemistry Research Campus Golm Potsdam Germany.
Institut für Chemie und Biochemie Freie Universität Berlin Berlin Germany.
Exploration (Beijing). 2021 Dec 16;1(3):20210063. doi: 10.1002/EXP.20210063. eCollection 2021 Dec.
A combination of photochemistry and proton coupled electron transfer (PCET) is a primary strategy employed by biochemical systems and synthetic chemistry to enable uphill reactions under mild conditions. Degenerate nanometer-sized n-type semiconductor nanoparticles (SCNPs) with the Fermi level above the bottom of the conduction band are strongly reducing and act more like metals than semiconductors. Application of the degenerate SCNPs is limited to few examples. Herein, we load microporous potassium poly(heptazine imide) (K-PHI) nanoparticles with electrons (e) and charge balancing protons (H) in an illumination phase using sacrificial agents. e/H in the K-PHI nanoparticles are weakly bound and therefore could be used in a range of PCET reactions in dark, such as generation of aryl radicals from aryl halides, ketyl radicals from ketones, and 6e/6H reduction of nitrobenzene to aniline. The integration of several features that until now were intrinsic for plants and natural photosynthesis into a transition metal free nanomaterial composed of abundant elements (C, N, and K) offers a powerful tool for synthetic organic chemistry.
光化学与质子耦合电子转移（PCET）相结合是生物化学系统和合成化学用于在温和条件下实现上坡反应的主要策略。费米能级高于导带底部的简并纳米级n型半导体纳米颗粒（SCNP）具有很强的还原性，其行为更像金属而非半导体。简并SCNP的应用实例有限。在此，我们在光照阶段使用牺牲剂将微孔聚（七嗪酰亚胺）钾（K-PHI）纳米颗粒负载电子（e）和电荷平衡质子（H）。K-PHI纳米颗粒中的e/H结合较弱，因此可用于一系列暗反应中的PCET反应，如由芳基卤化物生成芳基自由基、由酮生成酮基自由基以及将硝基苯6e/6H还原为苯胺。将迄今为止植物和自然光合作用所固有的几个特征整合到一种由丰富元素（C、N和K）组成的无过渡金属纳米材料中，为合成有机化学提供了一个强大的工具。
