Qin Qi, Wang Di, Shao Zhichao, Zhang Yingying, Zhang Qiang, Li Xinyue, Huang Chao, Mi Liwei
Center for Advanced Materials Research and Henan Key Laboratory of Functional Salt Materials, Zhongyuan University of Technology, Zhengzhou 450007, China.
ACS Appl Mater Interfaces. 2022 Aug 17;14(32):36845-36854. doi: 10.1021/acsami.2c09290. Epub 2022 Aug 8.
Regulating atomically precise sites in catalysts to achieve site-selective reactions is remarkable but challenging. In this work, a convenient and facile solid-gas/liquid reaction strategy was used to construct controllable active sites in metal-organic frameworks (MOFs) to guide an orientation site-selective reaction. A flexible Cu-MOF- with dynamics originating from an anionic and tailorable framework could undergo a reversible structural transformation to engineer a topologically equivalent mixed-valent CuCu-MOF- via a solid-gas/liquid oxidation/reduction process. More importantly, Cu-MOF- and CuCu-MOF- could further execute the solid-gas/liquid reaction under ammonia vapor/solution to generate Cu-MOF-. Furthermore, the transformation from Cu-MOF- to CuCu-MOF- and Cu-MOF- served as controllable catalysts to facilitate site-selective reactions to realize direct C-N bond arylations. The results demonstrated that Cu-MOF- and Cu-MOF- possessed well-defined platforms with uniformly and accurately active sites to attain a "turn-on/off" process via different reaction routes, providing the desired site-selective ring-opening products.
调控催化剂中的原子精确位点以实现位点选择性反应意义重大但颇具挑战。在这项工作中，采用了一种简便易行的固 - 气/液反应策略，在金属有机框架（MOF）中构建可控的活性位点，以引导定向位点选择性反应。一种具有源于阴离子且可定制框架的动力学的柔性铜基MOF（Cu - MOF - ），可通过固 - 气/液氧化/还原过程经历可逆的结构转变，从而设计出拓扑等效的混合价态CuCu - MOF - 。更重要的是，Cu - MOF - 和CuCu - MOF - 能够在氨蒸气/溶液下进一步进行固 - 气/液反应生成Cu - MOF - 。此外，从Cu - MOF - 到CuCu - MOF - 和Cu - MOF - 的转变作为可控催化剂，促进位点选择性反应以实现直接C - N键芳基化。结果表明，Cu - MOF - 和Cu - MOF - 拥有具有均匀且精确活性位点的明确平台，通过不同反应路线实现“开启/关闭”过程，从而提供所需的位点选择性开环产物。
