Periodic Tendril Perversion and Helices in the AMoO2F3 (A = K, Rb, NH4, Tl) Family

Justin C. Hancock; Matthew L. Nisbet; Weiguo Zhang; P. Shiv Halasyamani; Kenneth R. Poeppelmeier

doi:10.1021/jacs.0c01218

Periodic Tendril Perversion and Helices in the AMoO₂F₃ (A = K, Rb, NH₄, Tl) Family

Justin C. Hancock, Matthew L. Nisbet, Weiguo Zhang, P. Shiv Halasyamani, Kenneth R. Poeppelmeier^*

^*Corresponding author for this work

Chemistry

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

20 Scopus citations

Abstract

Although compounds of the formula AMoO₂F₃ (A = K, Rb, Cs, NH₄, Tl) have been known for decades, crystal structures have only been reported for CsMoO₂F₃ and NH₄MoO₂F₃. The three compounds (Rb/NH₄/Tl)MoO₂F₃ are isostructural and crystallize in the centrosymmetric space group C2/c (No. 15). The compounds contain the MoO₂F₃^- anionic chain, composed of corner-sharing MoO₂F₄ octahedra, with Mo⁶⁺ coordinated by two cis bridging fluoride anions that are trans to terminal oxide anions. The MoO₂F₃^- chain has a very unusual and complex chain structure; a single chain contains alternating zigzag and helical sections. These helical regions alternate in chirality along the chain, and thus the chains exhibit periodic tendril perversion. To the best of the authors' knowledge, no other materials with a similar chain structure have been reported. On the other hand, KMoO₂F₃ is noncentrosymmetric and chiral, crystallizing in the enantiomorphic space group P2₁2₁2₁ (No. 19). KMoO₂F₃ also contains the MoO₂F₃^- anionic chain. However, the chain is helical, with only one enantiomer present, resulting in a chiral, noncentrosymmetric structure.

Original language	English (US)
Pages (from-to)	6375-6380
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	142
Issue number	13
DOIs	https://doi.org/10.1021/jacs.0c01218
State	Published - Apr 1 2020

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.0c01218

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@article{20cf2e9f8c4045ef9ac58ea91b83dfda,

title = "Periodic Tendril Perversion and Helices in the AMoO2F3 (A = K, Rb, NH4, Tl) Family",

abstract = "Although compounds of the formula AMoO2F3 (A = K, Rb, Cs, NH4, Tl) have been known for decades, crystal structures have only been reported for CsMoO2F3 and NH4MoO2F3. The three compounds (Rb/NH4/Tl)MoO2F3 are isostructural and crystallize in the centrosymmetric space group C2/c (No. 15). The compounds contain the MoO2F3- anionic chain, composed of corner-sharing MoO2F4 octahedra, with Mo6+ coordinated by two cis bridging fluoride anions that are trans to terminal oxide anions. The MoO2F3- chain has a very unusual and complex chain structure; a single chain contains alternating zigzag and helical sections. These helical regions alternate in chirality along the chain, and thus the chains exhibit periodic tendril perversion. To the best of the authors' knowledge, no other materials with a similar chain structure have been reported. On the other hand, KMoO2F3 is noncentrosymmetric and chiral, crystallizing in the enantiomorphic space group P212121 (No. 19). KMoO2F3 also contains the MoO2F3- anionic chain. However, the chain is helical, with only one enantiomer present, resulting in a chiral, noncentrosymmetric structure.",

author = "Hancock, {Justin C.} and Nisbet, {Matthew L.} and Weiguo Zhang and Halasyamani, {P. Shiv} and Poeppelmeier, {Kenneth R.}",

note = "Funding Information: The authors thank Charlotte Stern for helpful discussions regarding the reported crystal structures. This work was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (J.C.H. and K.R.P.). This work was also supported by funding from the National Science Foundation under grant DMR-1904701 (M.L.N.). The single-crystal X-ray data measurements were acquired at Northwestern University{\textquoteright}s Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which is supported by grants from NSF-NSEC, NSF-MRSEC, the KECK Foundation, the State of Illinois, and Northwestern University. P.S.H. and W.Z. thank the Welch Foundation (Grant E-1457) for support. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

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doi = "10.1021/jacs.0c01218",

language = "English (US)",

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T1 - Periodic Tendril Perversion and Helices in the AMoO2F3 (A = K, Rb, NH4, Tl) Family

AU - Hancock, Justin C.

AU - Nisbet, Matthew L.

AU - Zhang, Weiguo

AU - Halasyamani, P. Shiv

AU - Poeppelmeier, Kenneth R.

N1 - Funding Information: The authors thank Charlotte Stern for helpful discussions regarding the reported crystal structures. This work was supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (J.C.H. and K.R.P.). This work was also supported by funding from the National Science Foundation under grant DMR-1904701 (M.L.N.). The single-crystal X-ray data measurements were acquired at Northwestern University’s Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which is supported by grants from NSF-NSEC, NSF-MRSEC, the KECK Foundation, the State of Illinois, and Northwestern University. P.S.H. and W.Z. thank the Welch Foundation (Grant E-1457) for support. Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/4/1

Y1 - 2020/4/1

N2 - Although compounds of the formula AMoO2F3 (A = K, Rb, Cs, NH4, Tl) have been known for decades, crystal structures have only been reported for CsMoO2F3 and NH4MoO2F3. The three compounds (Rb/NH4/Tl)MoO2F3 are isostructural and crystallize in the centrosymmetric space group C2/c (No. 15). The compounds contain the MoO2F3- anionic chain, composed of corner-sharing MoO2F4 octahedra, with Mo6+ coordinated by two cis bridging fluoride anions that are trans to terminal oxide anions. The MoO2F3- chain has a very unusual and complex chain structure; a single chain contains alternating zigzag and helical sections. These helical regions alternate in chirality along the chain, and thus the chains exhibit periodic tendril perversion. To the best of the authors' knowledge, no other materials with a similar chain structure have been reported. On the other hand, KMoO2F3 is noncentrosymmetric and chiral, crystallizing in the enantiomorphic space group P212121 (No. 19). KMoO2F3 also contains the MoO2F3- anionic chain. However, the chain is helical, with only one enantiomer present, resulting in a chiral, noncentrosymmetric structure.

AB - Although compounds of the formula AMoO2F3 (A = K, Rb, Cs, NH4, Tl) have been known for decades, crystal structures have only been reported for CsMoO2F3 and NH4MoO2F3. The three compounds (Rb/NH4/Tl)MoO2F3 are isostructural and crystallize in the centrosymmetric space group C2/c (No. 15). The compounds contain the MoO2F3- anionic chain, composed of corner-sharing MoO2F4 octahedra, with Mo6+ coordinated by two cis bridging fluoride anions that are trans to terminal oxide anions. The MoO2F3- chain has a very unusual and complex chain structure; a single chain contains alternating zigzag and helical sections. These helical regions alternate in chirality along the chain, and thus the chains exhibit periodic tendril perversion. To the best of the authors' knowledge, no other materials with a similar chain structure have been reported. On the other hand, KMoO2F3 is noncentrosymmetric and chiral, crystallizing in the enantiomorphic space group P212121 (No. 19). KMoO2F3 also contains the MoO2F3- anionic chain. However, the chain is helical, with only one enantiomer present, resulting in a chiral, noncentrosymmetric structure.

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DO - 10.1021/jacs.0c01218

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Periodic Tendril Perversion and Helices in the AMoO₂F₃ (A = K, Rb, NH₄, Tl) Family

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CSD 1992779: Experimental Crystal Structure Determination

CSD 1992777: Experimental Crystal Structure Determination

CSD 1992780: Experimental Crystal Structure Determination

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Periodic Tendril Perversion and Helices in the AMoO2F3 (A = K, Rb, NH4, Tl) Family

Abstract

ASJC Scopus subject areas

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CSD 1992779: Experimental Crystal Structure Determination

CSD 1992777: Experimental Crystal Structure Determination

CSD 1992780: Experimental Crystal Structure Determination

Cite this

Periodic Tendril Perversion and Helices in the AMoO₂F₃ (A = K, Rb, NH₄, Tl) Family