Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

Alexander Mutschke; Annika Schulz; Marko Bertmer; Clemens Ritter; Antti J. Karttunen; Gregor Kieslich; Nathalie Kunkel

doi:10.1039/d2sc01861f

Expanding the hydride chemistry: antiperovskites A₃MO₄H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

Alexander Mutschke^*
, Annika Schulz
, Marko Bertmer
, Clemens Ritter
, Antti J. Karttunen
, Gregor Kieslich
, Nathalie Kunkel

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

8 Citations (Scopus)

41 Downloads (Pure)

Abstract

The four compounds A₃MO₄H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb₃MoO₄D, Cs₃MoO₄D and Cs₃WO₄D crystallize in the antiperovskite-like K₃SO₄F-structure type, while Rb₃WO₄D adopts a different orthorhombic structure. ²H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb₃WO₄H shows a unique, peculiar valence band structure dominated by hydride states.

Original language	English
Pages (from-to)	7773–7779
Journal	Chemical Science
Volume	13
Issue number	26
DOIs	https://doi.org/10.1039/d2sc01861f
Publication status	Published - 25 May 2022
MoE publication type	A1 Journal article-refereed

Funding

The authors thank Christoph Wallach for Raman measurements and Sabine Zeitz for UV/Vis absorption spectroscopy. A. M. and M. B. thank Leonhard Dorsch for packing of the MAS rotors. Bircan Dilki is thanked gratefully for conducting the elemental analysis. We would like to thank the Institut Laue-Langevin for beam time allocated on D2B; https://doi.org/10.5291/ILL-DATA.5-21-1170 and https://doi.org/10.5291/ILL-DATA.EASY-725 . A. M. and N. K. thank the DFG for funding (project number 245845833) within International Research Training Group IRTG 2022—Alberta Technical University of Munich School for Functional Hybrid Materials (ATUMS). A. M. thanks the International Graduate School for Science and Engineering (IGSSE) for support. A. J. K. thanks Academy of Finland for funding (grant 324973) and CSC, the Finnish IT Center for Science for computational resources.

Access to Document

10.1039/d2sc01861fLicence: CC BY

Expanding the hydride chemistryFinal published version, 775 KBLicence: CC BY

Cite this

@article{ddc65581a18d44db98d191a1b49a3fdf,

title = "Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides",

abstract = "The four compounds A3MO4H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb3MoO4D, Cs3MoO4D and Cs3WO4D crystallize in the antiperovskite-like K3SO4F-structure type, while Rb3WO4D adopts a different orthorhombic structure. 2H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb3WO4H shows a unique, peculiar valence band structure dominated by hydride states.",

author = "Alexander Mutschke and Annika Schulz and Marko Bertmer and Clemens Ritter and Karttunen, \{Antti J.\} and Gregor Kieslich and Nathalie Kunkel",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry",

year = "2022",

month = may,

day = "25",

doi = "10.1039/d2sc01861f",

language = "English",

volume = "13",

pages = "7773–7779",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "26",

}

TY - JOUR

T1 - Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

AU - Mutschke, Alexander

AU - Schulz, Annika

AU - Bertmer, Marko

AU - Ritter, Clemens

AU - Karttunen, Antti J.

AU - Kieslich, Gregor

AU - Kunkel, Nathalie

PY - 2022/5/25

Y1 - 2022/5/25

N2 - The four compounds A3MO4H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb3MoO4D, Cs3MoO4D and Cs3WO4D crystallize in the antiperovskite-like K3SO4F-structure type, while Rb3WO4D adopts a different orthorhombic structure. 2H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb3WO4H shows a unique, peculiar valence band structure dominated by hydride states.

AB - The four compounds A3MO4H (A = Rb, Cs; M = Mo, W) are introduced as the first members of the new material class of the transition oxometalate hydrides. The compounds are accessible via a thermal synthesis route with carefully controlled conditions. Their crystal structures were solved by neutron diffraction of the deuterated analogues. Rb3MoO4D, Cs3MoO4D and Cs3WO4D crystallize in the antiperovskite-like K3SO4F-structure type, while Rb3WO4D adopts a different orthorhombic structure. 2H MAS NMR, Raman spectroscopy and elemental analysis prove the abundance of hydride ions next to oxometalate ions and experimental findings are supported by quantum chemical calculations. The tetragonal phases are direct and wide band gap semiconductors arising from hydride states, whereas Rb3WO4H shows a unique, peculiar valence band structure dominated by hydride states.

UR - https://www.scopus.com/pages/publications/85132728717

U2 - 10.1039/d2sc01861f

DO - 10.1039/d2sc01861f

M3 - Article

AN - SCOPUS:85132728717

SN - 2041-6520

VL - 13

SP - 7773

EP - 7779

JO - Chemical Science

JF - Chemical Science

IS - 26

ER -

Expanding the hydride chemistry: antiperovskites A₃MO₄H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

Abstract

Funding

Access to Document

Other files and links

Fingerprint

-: Experimental-quantum chemical characterization methods for ionic metal hydrides

Cite this

Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Projects

-: Experimental-quantum chemical characterization methods for ionic metal hydrides

Cite this

Expanding the hydride chemistry: antiperovskites A₃MO₄H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides