Yu Jipan, Zhao Chongyang, Zhou Rong, Gao Wenchao, Wang Shuai, Liu Kang, Chen Siyu, Hu Kongqiu, Mei Lei, Yuan Liyong, Chai Zhifang, Hu Hanshi, Shi Weiqun
Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Department of Chemistry, Key Laboratory of Organic Optoelectronics and, Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, P.R. China.
Chemistry. 2020 Dec 9;26(69):16521-16529. doi: 10.1002/chem.202003431. Epub 2020 Nov 3.
The development of the uranyl cation as a powerful photocatalyst is seriously delayed in comparison with the advances in its fundamental and structural chemistry. However, its characteristic high oxidative capability in the excited state ([UO ] * (+2.6 V vs. SHE; SHE=standard hydrogen electrode) combined with blue-light absorption (hv=380-500 nm) and a long-lived fluorescence lifetime up to microseconds have reveals that the uranyl cation approaches an ideal photocatalyst for visible-light-driven organic transformations. Described herein is the successful use of uranyl nitrate as a photocatalyst to enable C(sp )-H activation and C-C bond formation through hydrogen atom transfer (HAT) under blue-light irradiation. In particular, this operationally simple strategy provides an appropriate approach to the synthesis of diverse and valuable diarylmethane motifs. Mechanistic studies and DFT calculations have provided insights into the detailed mechanism of the photoinduced HAT pathway. This research suggests a general platform that could popularize promising uranyl photocatalytic performance.
与铀酰阳离子在基础化学和结构化学方面的进展相比，其作为一种强大光催化剂的发展严重滞后。然而，它在激发态具有的特征性高氧化能力（[UO] *（相对于标准氢电极（SHE）为 +2.6 V；SHE = 标准氢电极），结合蓝光吸收（hv = 380 - 500 nm）以及长达微秒级的长寿命荧光寿命，表明铀酰阳离子接近一种用于可见光驱动有机转化的理想光催化剂。本文描述了成功使用硝酸铀酰作为光催化剂，在蓝光照射下通过氢原子转移（HAT）实现C(sp) - H活化和C - C键形成。特别是，这种操作简单的策略为合成多样且有价值的二芳基甲烷基序提供了一种合适的方法。机理研究和密度泛函理论（DFT）计算为光诱导HAT途径的详细机理提供了见解。这项研究提出了一个通用平台，有望推广有前景的铀酰光催化性能。
