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Borohydride-containing coordination polymers: synthesis, air stability and dehydrogenation

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(4)...

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Detalles Bibliográficos
Autores principales: Kadota, Kentaro, Duong, Nghia Tuan, Nishiyama, Yusuke, Sivaniah, Easan, Kitagawa, Susumu, Horike, Satoshi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6585883/
https://www.ncbi.nlm.nih.gov/pubmed/31360426
http://dx.doi.org/10.1039/c9sc00731h
Descripción
Sumario: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(4)(–) has been demanded. For this purpose, we synthesize a series of BH(4)(–)-based coordination polymers/metal–organic frameworks. The reactivity of BH(4)(–) in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH(4))(2)(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(δ+)···H(δ–) 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, in situ synchrotron PXRD and solid-state NMR.