Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 18, Pages 7679-7689Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja210984k
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Funding
- National Science Foundation [DMR-1005827]
- Robert A. Welch Foundation [E-1457]
- W.M. Keck Foundation
- Northwestern University
- NIH
- Rice Foundation
- Robert H. Lurie Comprehensive Cancer Center
- NSF-NSEC
- NSF-MRSEC
- Keck Foundation
- state of Illinois
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [1005827] Funding Source: National Science Foundation
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A methodology for the design of polar, inorganic structures is demonstrated here with the packing of lambda (Lambda)-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 CuVOF4(H2O)(7): this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H2O)(5)](2+) cations and [VOF4(H2O)](2-) anions into Lambda-shaped, bimetallic BBUs to form CuVOF4(H2O)(6)center dot H2O, owing to the Jahn-Teller distortion of Cu2+. Conversely, the centrosymmetric heterotypes with the same formula MVOF4(H2O)(2) (M-II = Co, Ni, and Zn) exhibit ordered, isolated [VOF4(H2O)](2-) and [M(H2O)(6)](2+) ionic species in a hydrogen bond network CuVOF4(H2O)(7) exhibits a net polar moment while the heterotypes do not; this demonstrates that Lambda-shaped BBUs give a greater probability for and, in this case, lead to NCS structures.
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