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

ABSTRACT: 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 BH4 - has been demanded. For this purpose, we synthesize a series of BH4 --based coordination polymers/metal-organic frameworks. The reactivity of BH4 - in the structures is regulated by coordination geometry and neighboring ligands, and one of the compounds [Zn(BH4)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.

SUBMITTER: Kadota K

PROVIDER: S-EPMC6585883 | biostudies-other | 2019 Jun

REPOSITORIES: biostudies-other

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

Kadota Kentaro K Duong Nghia Tuan NT Nishiyama Yusuke Y Sivaniah Easan E Kitagawa Susumu S Horike Satoshi S

Chemical science 20190513 24

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 BH4 - has been demanded. For this purpose, we synthesize a series of BH4 --based coordination polymers/metal-organic frameworks. The reactivity of BH<su ...[more]

PMID: 31360426

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Project description:Five new Lanthanide(III) complexes of malonic acid (HOOC-CH2-COOH); {[Gd(C3H2O4)(H2O)4]·NO3} n (1), {[Tb(C3H2O4)(H2O)4]·NO3} n (2), {[Ho(C3H2O4)(H2O)4]·NO3} n (3), [Er(C3H2O4)(C3H3O4)(H2O)2] n (4), and {[Eu2(C3H2O4)2(C3H3O4)2(H2O)6]·4H2O} n (5) were synthesized and characterized by elemental, infrared spectral, and thermal analyses. The structures of compounds 1-5 were determined by single crystal X-ray diffraction technique. The X-ray analysis reveals that compounds 1, 2, and 3 are isostructural and crystallized in the orthorhombic space group Pmn21. The lanthanide(III) ions are coordinated by four carboxylate and four water oxygen atoms adopting a distorted square antiprism geometry. The LnO8 square antiprisms are linked into infinite layers by malonate (C3H2 O42- ) dianions sandwiching sheets of nitrate counter ions. Compound 4 contains ErO8 square antiprisms linked into a two-dimensional network by hydrogen malonate (C3H3 O4- ) anions and malonate dianions. The europium complex, 5 is dinuclear having the two europium(III) ions (Eu1 and Eu2) bridged by carboxylate groups of hydrogen malonate ligands. The europium ions in 5 are nine-coordinate and exhibit a distorted monocapped square antiprism geometry. All the structures are consolidated by O-H⋯ O hydrogen bonds. The photoluminescence spectra of 1-5 exhibit characteristic emissions in the visible region. The IR spectra and thermal data are consistent with the structural results. The room-temperature effective magnetic moments for 1-4 are in good agreement with those expected for the free ions, while the data for 5 indicates that low-lying excited states contribute to the observed moment. The compound 1 was further subjected to quantum computational calculations to explore its optoelectronic properties including; density of states (DOS), dielectric function, refractive index, extinction coefficient, and absorption spectrum, to highlight the possible applications of such materials in the optoelectronics.

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

Publications

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

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