Pillared Metal–Organic Framework Initiating Intermolecular Atom-Transfer Radical Addition via Visible-Light-Induced Electron Transfer Activation of Haloalkanes,ACS Applied Materials & Interfaces

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Pillared Metal–Organic Framework Initiating Intermolecular Atom-Transfer Radical Addition via Visible-Light-Induced Electron Transfer Activation of Haloalkanes
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2021-07-16 , DOI: 10.1021/acsami.1c06391
Xin Liu ₁ , Zhifen Guo ₁ , Yan Che ₁ , Rong Bai ₁ , Yanhong Chi ₁ , Chunyi Guo ₁ , Hongzhu Xing ₁

Affiliation

Herein, a novel metal–organic framework (MOF) with a pillared-layer structure was rationally synthesized to initiate intermolecular atom-transfer radical addition (ATRA) via photoinduced electron transfer activation of haloalkanes. The MOF synthesized via the controllable pillared-layer method is of excellent visible-light absorption and high chemical stability. Photocatalytic experiments show the atom transfer of various alkyl halides (R–X, X = Cl/Br/I) onto diverse olefins was successfully achieved to produce functional ATRA products. The mechanism and experimental investigations reveal the prepared MOF serves as an efficient photocatalyst with strong reduction potential to activate haloalkane substrates via photoinduced electron transfer, generating a highly reactive alkyl radical to trigger the ATRA reaction. Key events in the ATRA reaction, including alkyl radical photogeneration as well as halide transfer, have been further regulated to achieve preferable photocatalytic performance with higher yields, shorter reaction time, and desirable cycling capability. It is notable that the work is the first report on photoinduced electron transfer activation of halides by a MOF photocatalyst for the ATRA reaction, providing a new blueprint for MOFs to develop photoinduced radical reactions.

中文翻译：

柱状金属-有机骨架通过卤代烷烃的可见光诱导电子转移活化引发分子间原子转移自由基加成

在此，我们合理合成了一种具有柱层结构的新型金属有机骨架（MOF），以通过卤代烷烃的光诱导电子转移活化引发分子间原子转移自由基加成（ATRA）。通过可控柱撑层法合成的MOF具有优异的可见光吸收和高化学稳定性。光催化实验表明，各种烷基卤化物（R-X，X = Cl/Br/I）的原子转移已成功实现到各种烯烃上，以生产功能性 ATRA 产品。机理和实验研究表明，所制备的 MOF 作为一种高效的光催化剂，具有很强的还原电位，可通过光诱导电子转移激活卤代烷烃底物，产生高活性烷基自由基以触发 ATRA 反应。ATRA反应中的关键事件，包括烷基自由基光生成和卤化物转移，已被进一步调节以实现具有更高产率、更短反应时间和理想循环能力的优选光催化性能。值得注意的是，该工作是第一份关于通过 MOF 光催化剂对卤化物进行光诱导电子转移激活 ATRA 反应的报告，为 MOF 开发光诱导自由基反应提供了新的蓝图。

更新日期：2021-07-28

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