文献类型：期刊文献

英文题名：Photo-Induced Active Lewis Acid-Base Pairs in a Metal-Organic Framework for H2 Activation

作者：Ng, Bryan Kit Yue[1];Zhou, Zi-Jian[2,3];Liu, Ting-Ting[2,3];Yoskamtorn, Tatchamapan[1];Li, Guangchao[1];Wu, Tai-Sing[4];Soo, Yun-Liang[5];Wu, Xin-Ping[2,3];Tsang, Shik Chi Edman[1]

机构：[1]Univ Oxford, Dept Chem, Oxford OX1 3QR, England;[2]East China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, Shanghai 200237, Peoples R China;[3]East China Univ Sci andTechnol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Natl Synchrotron Radiat Res Ctr, Hsinchu 30076, Taiwan;[5]Natl Tsing Hua Univ, Dept Phys, Hsinchu 30013, Taiwan

年份：2023

卷号：145

期号：35

起止页码：19312

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20233614694380);WOS:【SCI-EXPANDED(收录号:WOS:001063537200001)】；

基金：This project was funded by the EPSRC, UK and the theoretical calculations were financially supported by the National Natural Science Foundation of China (22003016) and Shanghai Sailing Program (20YF1410000). The theoretical calculations were carried out at National Supercomputer Center in Tianjin, and this research was also supported by TianHe Qingsuo Project-special fund project.

语种：英文

外文关键词：Charge transfer - Density functional theory - Organometallics - Ruthenium compounds

摘要：The establishment of active sites as the frustrated Lewis pair (FLP) has recently attracted much attention ranging from homogeneous to heterogeneous systems in the field of catalysis. Their unquenched reactivity of Lewis acid and base pairs in close proximity that are unable to form stable adducts has been shown to activate small molecules such as dihydrogen heterolytically. Herein, we show that grafted Ru metal-organic framework-based catalysts prepared via N-containing linkers are rather catalytically inactive for H-2 activation despite the application of elevated temperatures. However, upon light illumination, charge polarization of the anchored Ru bipyridine complex can form a transient Lewis acid-base pair, Ru+-N- via metal-to-ligand charge transfer, as confirmed by time-dependent density functional theory (TDDFT) calculations to carry out effective H-2-D-2 exchange. FTIR and 2-D NMR endorse the formation of such reactive intermediate(s) upon light irradiation.