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New Molybdenum(VI) Phosphates: Synthesis, Characterization, and Calculations of Centrosymmetric RbMoO2PO4 and Noncentrosymmetric Rb4Mo5P2O22

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† Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, 40-1 South Beijing Road, Urumqi 830011, China
‡ University of Chinese Academy of Sciences, Beijing 100049, China
*Phone: (86)991-3674558. Fax: (86)991-3838957. E-mail: [email protected] (S.P.), [email protected] (Z.Y.).
Cite this: Inorg. Chem. 2013, 52, 3, 1488–1495
Publication Date (Web):January 15, 2013
https://doi.org/10.1021/ic302246c
Copyright © 2013 American Chemical Society
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Abstract

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Two new molybdenum(VI) phosphates, RbMoO2PO4 and Rb4Mo5P2O22, have been synthesized by standard solid-state reactions, and their structures were determined by single-crystal X-ray diffraction. The former is centrosymmetric, whereas the latter is noncentrosymmetric and chiral. Their crystal structures both consist of corner- and edge-shared MoO6 octahedra, PO4 tetrahedra, and RbOn (n = 8 or 10) polyhedra and exhibit three- and one-dimensional structures, respectively. Powder second-harmonic generation (SHG) measurements revealed an SHG efficiency of approximately 1.4 × KH2PO4 (KDP) for Rb4Mo5P2O22. Thermal analysis, infrared and UV–vis-NIR diffuse reflectance spectroscopy, and electronic band structure calculations were also performed on the reported materials. Crystal data are the following: RbMoO2PO4, orthorhombic, space group Fddd (No. 70), a = 11.012(5) Å, b = 12.403(5) Å, c = 15.839(7) Å, V = 2163.3(16) Å3, and Z = 16; Rb4Mo5P2O22, orthorhombic, space group C2221 (No. 20), a = 6.5300(5) Å, b = 19.7834(18) Å, c = 17.3451(15) Å, V = 2240.7(3) Å3, and Z = 4.

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X-ray data in CIF format, atomic coordinates and equivalent isotropic displacement parameters, powder XRD patterns, TGA and DSC diagrams, IR and UV–vis-NIR diffuse-reflectance spectra, phase-matching diagrams, and electronic band structures patterns. This material is available free of charge via the Internet at http://pubs.acs.org.

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This article is cited by 26 publications.

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  2. Tuohetijiang Baiheti, Shujuan Han, Abudukadi Tudi, Zhihua Yang, Shilie Pan. Alignment of Polar Moieties Leading to Strong Second Harmonic Response in KCsMoP2O9. Chemistry of Materials 2020, 32 (7) , 3297-3303. https://doi.org/10.1021/acs.chemmater.0c00610
  3. Yahui Li, Guopeng Han, Hongwei Yu, Hao Li, Zhihua Yang, Shilie Pan. Two Polar Molybdenum(VI) Iodates(V) with Large Second-Harmonic Generation Responses. Chemistry of Materials 2019, 31 (8) , 2992-3000. https://doi.org/10.1021/acs.chemmater.9b00521
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  14. Yuan Fang, Zhaohui Chen, Yunjing Shi, Wenyao Zhang, Xiaoyu Dong. Li1.52Na4.48Cd8(PO4)2(P2O7)4: A new mixed-anion diphosphate containing four types of dimensions groups. Inorganic Chemistry Communications 2017, 86 , 253-257. https://doi.org/10.1016/j.inoche.2017.09.007
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  16. Tong-Ying Chang, Chun-Li Hu, Dong Yan, Jiang-Gao Mao. (H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 and Ba 2 Cd 3 (PO 4 ) 2 (HPO 4 ) 2 : Syntheses, crystal structures and characterizations of two mixed metal phosphates. Journal of Solid State Chemistry 2017, 251 , 19-25. https://doi.org/10.1016/j.jssc.2017.04.008
  17. Meng-Shu Liu, Wei-Dong Yu, Qian-Wen Yan, Jun Yan. Introducing Chirality into Hybrid Clusters from an Achiral Ligand: Synthesis and Characterization of Polyoxomolybdates Containing a Benzylarsonate Group. European Journal of Inorganic Chemistry 2017, 2017 (13) , 1947-1950. https://doi.org/10.1002/ejic.201700265
  18. Wei-Long Zhang, Hao Zhang, Zhang-Zhen He, Wen-Dan Cheng. Syntheses, structural and characterizations of a new anhydrous mixed-metal phosphate. Inorganica Chimica Acta 2016, 449 , 9-13. https://doi.org/10.1016/j.ica.2016.04.036
  19. Yujiao Hou, Haiyan An, Tieqi Xu, Sangen Zhao, Junhua Luo. Chiral polyoxomolybdate-based hybrid compounds obtained by spontaneous resolution: syntheses, structures and non-linear optical properties. New Journal of Chemistry 2016, 40 (12) , 10316-10324. https://doi.org/10.1039/C6NJ02709A
  20. Xiangyu Zhang, Danni Li, Zhihua Yang, Hongping Wu, Shilie Pan. Synthesis, Crystal Structure, and Properties of the Sodium Molybdate Fluoride Na 3 MoO 4 F. Zeitschrift für anorganische und allgemeine Chemie 2015, 641 (5) , 922-926. https://doi.org/10.1002/zaac.201500025
  21. Shengshi Huang, Qun Jing, Jian Han, Shilie Pan, Hongping Wu, Zhihua Yang. Three Alkali Metal Lead Orthophosphates - Syntheses, Crystal Structures and Properties of APbPO 4 (A = K, Rb, Cs). European Journal of Inorganic Chemistry 2015, 2015 (9) , 1490-1495. https://doi.org/10.1002/ejic.201403244
  22. Shujuan Han, Ying Wang, Qun Jing, Hongping Wu, Shilie Pan, Zhihua Yang. Effect of the cation size on the framework structures of magnesium tungstate, A 4 Mg(WO 4 ) 3 (A = Na, K), R 2 Mg 2 (WO 4 ) 3 (R = Rb, Cs). Dalton Transactions 2015, 44 (12) , 5810-5817. https://doi.org/10.1039/C5DT00332F
  23. Shengshi Huang, Hongwei Yu, Jian Han, Shilie Pan, Qun Jing, Ying Wang, Lingyun Dong, Hongping Wu, Zhihua Yang, Xian Wang. The Effect of the Ratio of [M/(B+P)] on the Configuration of Anionic Groups: Synthesis of the Borate-Phosphate LiPb 4 (BO 3 )(PO 4 ) 2. European Journal of Inorganic Chemistry 2014, 2014 (22) , 3467-3473. https://doi.org/10.1002/ejic.201402389
  24. Chunyan Bai, Chen Lei, Shilie Pan, Ying Wang, Zhihua Yang, Shujuan Han, Hongwei Yu, Yun Yang, Fangyuan Zhang. Syntheses, structures and characterizations of Rb3Na(MO4)2 (M = Mo, W) crystals. Solid State Sciences 2014, 33 , 32-37. https://doi.org/10.1016/j.solidstatesciences.2014.04.011
  25. Zheng Wang, Min Zhang, Shilie Pan, Zhihua Yang, Hui Zhang, Bingbing Zhang, Ying Wang, Jing Kang, Xiaoxia Lin. Exploring the influence of cationic skeletons on the arrangement of isolated BO 3 groups based on RbMgBO 3 , CsZn 4 (BO 3 ) 3 and Cs 4 Mg 4 (BO 3 ) 4. New J. Chem. 2014, 38 (7) , 3035-3041. https://doi.org/10.1039/C4NJ00363B
  26. Ying Wang, Shilie Pan, Xin Su, Zhihua Yang, Lingyun Dong, Min Zhang. ChemInform Abstract: New Molybdenum(VI) Phosphates: Synthesis, Characterization, and Calculations of Centrosymmetric RbMoO 2 PO 4 and Noncentrosymmetric Rb 4 Mo 5 P 2 O 22 .. ChemInform 2013, 44 (16) , no-no. https://doi.org/10.1002/chin.201316017

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