Kadota Kentaro, Duong Nghia Tuan, Nishiyama Yusuke, Sivaniah Easan, Kitagawa Susumu, Horike Satoshi
Department of Molecular Engineering , Graduate School of Engineering , Kyoto University , Katsura, Nishikyo-ku , Kyoto 615-8510 , Japan.
RIKEN-JEOL Collaboration Center , Tsurumi , Yokohama , Kanagawa 230-0045 , Japan.
Chem Sci. 2019 May 13;10(24):6193-6198. doi: 10.1039/c9sc00731h. eCollection 2019 Jun 28.
Control of the reactivity of hydride (H) in crystal structures has been a challenge because of its strong electron-donating ability and reactivity with protic species. For metal borohydrides, the dehydrogenation activity and air stability are in a trade-off, and control of the reactivity of BH has been demanded. For this purpose, we synthesize a series of BH -based coordination polymers/metal-organic frameworks. The reactivity of BH in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH)(dipyridylpropane)] exhibits both high dehydrogenation reactivity (1.4 wt% at 179 °C) and high air stability (50 RH% at 25 °C, 7 days). Single crystal X-ray diffraction analysis reveals that H ···H dihydrogen interactions and close packing of hydrophobic ligands are the key for the reactivity and stability. The dehydrogenation mechanism is investigated by temperature-programmed desorption, synchrotron PXRD and solid-state NMR.
由于氢化物（H）具有很强的给电子能力且能与质子性物种发生反应，因此控制其在晶体结构中的反应活性一直是一项挑战。对于金属硼氢化物而言，脱氢活性和空气稳定性存在权衡，人们一直要求控制BH的反应活性。为此，我们合成了一系列基于BH的配位聚合物/金属有机框架。结构中BH的反应活性通过配位几何结构和相邻配体进行调节，其中一种化合物[Zn(BH)(二吡啶丙烷)]兼具高脱氢反应活性（179°C时为1.4 wt%）和高空气稳定性（25°C、相对湿度50%条件下放置7天）。单晶X射线衍射分析表明，H···H双氢键相互作用和疏水配体的紧密堆积是反应活性和稳定性的关键。通过程序升温脱附、同步辐射PXRD和固态NMR对脱氢机理进行了研究。
