The role of polar, lamdba (λ)-shaped building units in noncentrosymmetric inorganic structures

Martin D. Donakowski, Romain Gautier, Jeongho Yeon, Donald T. Moore, Juan C. Nino, P. Shiv Halasyamani, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

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Abstract

A methodology for the design of polar, inorganic structures is demonstrated here with the packing of lambda (λ)-shaped basic building units (BBUs). Noncentrosymmetric (NCS) solids with interesting physical properties can be created with BBUs that lack an inversion center and are likely to pack into a polar configuration; previous methods to construct these solids have used NCS octahedra as BBUs. Using this methodology to synthesize NCS solids, one must increase the coordination of the NCS octahedra with maintenance of the noncentrosymmetry of the bulk. The first step in this progression from an NCS octahedron to an inorganic NCS solid is the formation of a bimetallic BBU. This step is exemplified with the compound CuVOF 4(H 2O) 7: this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H 2O) 5] 2+ cations and [VOF 4(H 2O)] 2- anions into λ-shaped, bimetallic BBUs to form CuVOF 4(H 2O) 6· H 2O, owing to the Jahn-Teller distortion of Cu 2+. Conversely, the centrosymmetric heterotypes with the same formula MVOF 4(H 2O) 7 (M II = Co, Ni, and Zn) exhibit ordered, isolated [VOF 4(H 2O)] 2- and [M(H 2O) 6] 2+ ionic species in a hydrogen bond network. CuVOF 4(H 2O) 7 exhibits a net polar moment while the heterotypes do not; this demonstrates that λ-shaped BBUs give a greater probability for and, in this case, lead to NCS structures.

Original languageEnglish
Pages (from-to)7679-7689
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number18
DOIs
Publication statusPublished - May 9 2012

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Anions
Cations
Hydrogen
Maintenance
Jahn-Teller effect
Hydrogen bonds
Negative ions
Physical properties
Positive ions

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

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The role of polar, lamdba (λ)-shaped building units in noncentrosymmetric inorganic structures. / Donakowski, Martin D.; Gautier, Romain; Yeon, Jeongho; Moore, Donald T.; Nino, Juan C.; Halasyamani, P. Shiv; Poeppelmeier, Kenneth R.

In: Journal of the American Chemical Society, Vol. 134, No. 18, 09.05.2012, p. 7679-7689.

Research output: Contribution to journalArticle

Donakowski, Martin D. ; Gautier, Romain ; Yeon, Jeongho ; Moore, Donald T. ; Nino, Juan C. ; Halasyamani, P. Shiv ; Poeppelmeier, Kenneth R. / The role of polar, lamdba (λ)-shaped building units in noncentrosymmetric inorganic structures. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 18. pp. 7679-7689.
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abstract = "A methodology for the design of polar, inorganic structures is demonstrated here with the packing of lambda (λ)-shaped basic building units (BBUs). Noncentrosymmetric (NCS) solids with interesting physical properties can be created with BBUs that lack an inversion center and are likely to pack into a polar configuration; previous methods to construct these solids have used NCS octahedra as BBUs. Using this methodology to synthesize NCS solids, one must increase the coordination of the NCS octahedra with maintenance of the noncentrosymmetry of the bulk. The first step in this progression from an NCS octahedron to an inorganic NCS solid is the formation of a bimetallic BBU. This step is exemplified with the compound CuVOF 4(H 2O) 7: this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H 2O) 5] 2+ cations and [VOF 4(H 2O)] 2- anions into λ-shaped, bimetallic BBUs to form CuVOF 4(H 2O) 6· H 2O, owing to the Jahn-Teller distortion of Cu 2+. Conversely, the centrosymmetric heterotypes with the same formula MVOF 4(H 2O) 7 (M II = Co, Ni, and Zn) exhibit ordered, isolated [VOF 4(H 2O)] 2- and [M(H 2O) 6] 2+ ionic species in a hydrogen bond network. CuVOF 4(H 2O) 7 exhibits a net polar moment while the heterotypes do not; this demonstrates that λ-shaped BBUs give a greater probability for and, in this case, lead to NCS structures.",
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