The Role of Polar, Lamdba (Λ)-Shaped Building Units in Noncentrosymmetric Inorganic Structures
- 15 February 2012
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (18), 7679-7689
- https://doi.org/10.1021/ja210984k
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(2)O)(7): this compound, presented here, crystallizes in an NCS structure with ordered, isolated [Cu(H(2)O)(5)](2+) cations and [VOF(4)(H(2)O)](2-) anions into Λ-shaped, bimetallic BBUs to form CuVOF(4)(H(2)O)(6)·H(2)O, owing to the Jahn-Teller distortion of Cu(2+). Conversely, the centrosymmetric heterotypes with the same formula MVOF(4)(H(2)O)(7) (M(II) = Co, Ni, and Zn) exhibit ordered, isolated [VOF(4)(H(2)O)](2-) and [M(H(2)O)(6)](2+) ionic species in a hydrogen bond network. CuVOF(4)(H(2)O)(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.Keywords
This publication has 66 references indexed in Scilit:
- New Layered Oxide-Fluoride Perovskites: KNaNbOF5 and KNaMO2F4 (M = Mo6+, W6+)Crystals, 2011
- Molecular design of nonlinear optical polymer based on DCM to enhance the NLO efficiency and thermal stabilityJournal of Polymer Science Part A: Polymer Chemistry, 2009
- Determination of absolute structure using Bayesian statistics on Bijvoet differencesJournal of Applied Crystallography, 2008
- A short history of SHELXActa Crystallographica Section A Foundations of Crystallography, 2007
- Novel Vanadium(IV) Oxyfluorides with ‘Spin-Ladder'-Like Structures, and Their Relationship to (VO)2P2O7Inorganic Chemistry, 2007
- Enhanced Temporal Stability of an NLO Polyurethane via a Two-Dimensional ChromophoreMacromolecular Rapid Communications, 2001
- Supramolecular Structures – Reason and ImaginationActa Crystallographica Section A Foundations of Crystallography, 1998
- Symptoms and treatment of hydrogen fluoride injuriesJournal of Fluorine Chemistry, 1996
- The Crystal Structure of DL-Alanine. II. Revision of Parameters by Three-Dimensional Fourier Analysis1Journal of the American Chemical Society, 1950
- The Crystal Structure of dl-AlanineJournal of the American Chemical Society, 1941