Structure-Directing Effect of Alkali Metal Cations in New Molybdenum Selenites, Na2Mo2O5(SeO3)(2), K2Mo2O5(SeO3)(2), and Rb2Mo3O7(SeO3)(3)
- Authors
- Bang, Seong-eun; Ok, Kang Min
- Issue Date
- Sep-2015
- Publisher
- AMER CHEMICAL SOC
- Citation
- INORGANIC CHEMISTRY, v.54, no.17, pp 8832 - 8839
- Pages
- 8
- Journal Title
- INORGANIC CHEMISTRY
- Volume
- 54
- Number
- 17
- Start Page
- 8832
- End Page
- 8839
- URI
- https://scholarworks.bwise.kr/cau/handle/2019.sw.cau/9114
- DOI
- 10.1021/acs.inorgchem.5b01588
- ISSN
- 0020-1669
1520-510X
- Abstract
- Both single crystals and pure polycrystalline samples of three new quaternary alkali metal molybdenum selenites, Na2Mo2O5(SeO3)(2), K2Mo2O5(SeO3)(2), and Rb2Mo3O7(SeO3)(3), have been synthesized through hydrothermal and solid-state reactions using A(2)CO(3) (A = Na, K, and Rb), MoO3, and SeO2 as reagents. The frameworks of all three materials consist of both families of second-order Jahn-Teller distortive cations, i.e., the d(0) cation (Mo6+) and the lone pair cation (Se4+). Although the extent of framework distortions and the resulting occupation sites of alkali metal cations are dissimilar, Na2Mo2O5(SeO3)(2) and K2Mo2O5(SeO3)(2) exhibit similar three-dimensional networks that are composed of highly asymmetric Mo2O11 dimers and SeO3 polyhedra. Rb2Mo3O7(SeO3)(3) reveals a two-dimensional structure that is built with Mo3O15 trimers and SeO3 intralayer linkers. Close structural examinations suggest that the structure-directing effect of alkali metal cations is significant in determining the framework distortions and the dimensions of the molybdenum selenites. UV-vis diffuse reflectance and infrared spectroscopy, thermogravimetric analyses, and ion-exchange reactions are reported, as are out-of-center distortion and dipole moment calculations.
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