Photo-Induced Active Lewis Acid-Base Pairs in a Metal-Organic Framework for H(2) Activation.
Photo-Induced Active Lewis Acid-Base Pairs in a Metal-Organic Framework for H(2) Activation.
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DOI：
10.1021/jacs.3c05244
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发表时间：
2023-09-06
影响因子：
15
通讯作者：
Tsang, Shik Chi Edman
中科院分区：
文献类型：
--
作者：
Ng, Bryan Kit Yue;Zhou, Zi-Jian;Liu, Ting-Ting;Yoskamtorn, Tatchamapan;Li, Guangchao;Wu, Tai-Sing;Soo, Yun-Liang;Wu, Xin-Ping;Tsang, Shik Chi Edman
作为阻挫刘易斯对（FLP）的活性中心的建立近年来在催化领域引起了从均相到多相体系的广泛关注。它们的刘易斯酸和不能形成稳定加合物的碱基对的非淬灭反应性已被证明能异相激活小分子如二氢。在此，我们表明，接枝Ru金属有机骨架为基础的催化剂，通过含N的连接体制备的是，而催化活性的H2活化，尽管高温下的应用。然而，在光照下，锚定的Ru联吡啶络合物的电荷极化可以通过金属到配体的电荷转移形成瞬时的刘易斯酸碱对Ru+-N-，如通过时间依赖的密度泛函理论（TDDFT）计算所证实的，以进行有效的H2-D2交换。FTIR和2-D NMR证实了在光照射下形成这种反应性中间体。
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 H2 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 H2–D2 exchange. FTIR and 2-D NMR endorse the formation of such reactive intermediate(s) upon light irradiation.
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