Hou Leixin, Jing Xu, Huang Huilin, Duan Chunying
State Key Laboratory of Fine Chemicals, Zhang Dayu College of Chemistry, Dalian University of Technology, Dalian 116024, P.R. China.
ACS Appl Mater Interfaces. 2022 Apr 6;14(13):15307-15316. doi: 10.1021/acsami.2c01595. Epub 2022 Mar 28.
Utilization of multiphotons to achieve high reduction potentials is a highly demanding but still challenging task for reductive cleavage of inert bonds. Herein, we report a new charge transfer approach that simultaneously excites the electron-rich dye and the radical anionic of the electron-deficient one for photocatalytic activation of aryl chlorides with high reduction potentials ( ≈ -1.9 to -2.9 V). Interactions between the tetraphenylbenzene-1,4,-diamine dyes in the large pores of metal-organic frameworks and the adsorbed 9,10-dicyanoanthracene partly endows charge transfer in the ground state. The first photoexcitation led to the formation charge separation pairs containing both radical cation and anion for second photon excitation. The possibility of modifying each absorption band of the two dyes independently innovated the resultant aryl radicals applied in various useful transformations, expanding multiphoton manifolds on both the dye scopes and reaction versions. A comparison of the catalytic performance between different structural patterns of metal-organic frameworks with the same ligand demonstrated that the incorporating of the organic dyes within the pores of the frameworks was essential to form charge-transfer species and accelerate the interesting chemical conversion.
利用多光子实现高还原电位是一项要求极高但仍具挑战性的任务，用于惰性键的还原裂解。在此，我们报道了一种新的电荷转移方法，该方法同时激发富电子染料和缺电子染料的自由基阴离子，用于光催化活化具有高还原电位（约 -1.9 至 -2.9 V）的芳基氯化物。金属有机框架大孔中的四苯基苯 -1,4,-二胺染料与吸附的 9,10 - 二氰基蒽之间的相互作用部分赋予了基态下的电荷转移。首次光激发导致形成包含自由基阳离子和阴离子的电荷分离对，用于二次光子激发。独立修饰两种染料各自吸收带的可能性，创新性地将所得芳基自由基应用于各种有用的转化中，在染料范围和反应类型两方面扩展了多光子体系。对具有相同配体的不同结构模式的金属有机框架之间的催化性能进行比较表明，在框架孔内掺入有机染料对于形成电荷转移物种和加速有趣的化学转化至关重要。
