Photo-induced active lewis acid-base pairs in metal-organic framework for H2 activation Bryan Kit Yue Ng 1 , Xin-Ping Wu 2 , Shik Chi Edman Tsang 1* 1 Department of Chemistry, University of Oxford, IK, 2 Key Laboratory for Advance Materials, East China University of Science and Technology, China The establishment of active sites as Frustrated Lewis Pair (FLP) has recently attracted much attention 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 shown to be able to activate small molecules such as dihydrogen heterolytically. Herein, by utilising the chemical stability and wide tuneability of UiO series metal-organic frameworks, we demonstrate that grafted Ru metal-organic framework-based catalysts prepared via N-containing linkers are rather catalytically inactive for H2 activation despite the application of elevated temperatures. However, upon light illumination, charge polarization of anchored Ru bipyridine complex can form transient Lewis acid-base pair, Ru+-N- via metal-to-ligand charge transfer, and this is confirmed by time- dependent density functional theory (TDDFT) calculations to carry out effective H2-D2 exchange. FTIR and 2-D NMR endorse the formation of such reactive intermediate(s) upon light irradiation. References
1. Ng, B. K. Y.; Wu, X.-P.; Tsang, S. C. E. et. al., J. Am. Chem. Soc. 2023 , 145, 35, 19312–19320 2. Leung, K. C.; Ng, B. K. Y.; Tsang, S. C. E. et. al., J. Am. Chem. Soc . 2023 , 145, 26, 14548–14561
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© The Author(s), 2023
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