Skip to main content
SpringerLink
Log in

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

A two-dimensional network compound [Ce(DMF)4(H2O)][α-BW12O40]·H2O·(HDMA)2 (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H5BW12O40·nH2O, Ce(NO3)3·6H2O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P21/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R 1 = 0.07710, wR 2 = 0.1416. Structural analysis indicates that every [Ce(DMF)4(H2O)]3+ building block is surrounded by three adjacent [α-BW12O40]5− polyanions, meanwhile, every [α-BW12O40]5− polyanion interconnects with three neighboring [Ce(DMF)4(H2O)]3+ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560°C. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4–7 media.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Guo Y H, Hu C W, Wang X L, et al. Microporous polyoxometalate POMs/SiO2: Synthesis and photocatalytic degradation of aqueous organocholorine pesticides. Chem Mater, 2000, 12: 3501–3508

    Article  CAS  Google Scholar 

  2. Wang Y H, Hu C W, Wang E B, et al. Synthesis and crystal structure of a novel amino-acid-containing polyoxometalate: K6[Cu(Ala)2·H2O]2[Cu(H2O)2(AsW9O34)2]·16H2O. Chem J Chin Uni(in Chinese), 2001, 22(3): 362

    CAS  Google Scholar 

  3. Coronado E, Gomez-Garcia C J. Polyoxometalate-based molecular materials. Chem Rev, 1998, 98: 273–296

    Article  CAS  Google Scholar 

  4. Guo Y H, Hu C W, Wang X L, et al. Microporous decatungstates: Synthesis and photochemical behavior. Chem Mater, 2001, 13: 4058–4064

    Article  CAS  Google Scholar 

  5. Peng J, Wang E B, Zhou Y S, et al. Synthesis, electrical properties and crystal structure of a new radical-ion salt based on Π-extended bis(TTF) and a Keggin heteropolymolybdate. J Chem Soc Dalton Trans, 1998, 3865

  6. Le Magneres P, Ouahab L, Golben S, et al. Diamagnetic and paramagnetic Keggin polyoxometalate salts containing 1-D and 3-D decamethylferrocenium network: Preparation, crystal structures and magnetic properties of [Fe(C5HMe5)2]4(POM)(solv)n (POM = [SiMo12O40]4−, [SiW12O40]4−, [PMo12O40]3−; solv = H2O, C3H7ON, CH3CN). Inorg Chem, 1974, 33: 5180

    Article  Google Scholar 

  7. Xu B, Wei Y, Barnes C L, et al. Hybrid molecular materials based on covalently linked inorganic polyoxometalates and organic conjugated systems. Angew Chem Int Ed, 2001, 40(12): 2290

    Article  CAS  Google Scholar 

  8. Wu C D, Lu C Z, Zhuang H H, et al. Hydrothermal assembly of a novel three-dimensional framework formed by [GdMo12O42]9− anions and nine coordinated GdIII cations. J Am Chem Soc, 2002, 124: 3836

    Article  CAS  Google Scholar 

  9. Lu M, Wei Y, Cheung C F C, et al. Hybrid molecular dumbbells: Bridging polyoxometalate clusters with an organic π-conjugated rod. Angew Chem Int Ed, 2002, 41(9): 1566

    Article  CAS  Google Scholar 

  10. Müller A, Beckman E, Hartmut B, et al. Inorganic chemistry goes protein size: A Mo368 nano-hedgehog initiating nanochemistry by symmetry breaking. Angew Chem Int Ed, 2002, 41(7): 1162

    Article  Google Scholar 

  11. Wang X, Liu L, Zhang G, et al. Protein-calixarene interactions: Complexation of bovine serum albumin by sulfonatocalix[n]arenas. J Chem Commun, 2001: 2472

  12. Khan M I, Yohannes E, Powell D. Vanadium oxide clusters as building blocks for the synthesis of metal oxide surfaces and framework materials: Synthesis and X-ray crystal structure of [H6Mn3VIV 15VV 4O46(H2O)12]·30H2O. Inorg Chem, 1999, 38: 212–213

    Article  CAS  Google Scholar 

  13. Choi H, Kwon Y U, Han O H. Nanocomposite gels between [V10O28]6− and [AlO4Al12(OH)24(H2O)12]7+ polyoxometalate clusters. Chem Mater, 1999, 11: 1641–1643

    Article  CAS  Google Scholar 

  14. Beauvais L G, Shores M P, Long J R. Cryano-bridged Re6Q8 (Q= S, Se) cluster-metal framework solids: A new class of porous materials. Chem Mater, 1998, 10: 3783–3786

    Article  CAS  Google Scholar 

  15. Shores M P, Beauvais L G, Long J R. Cluster-expanded Prussian blue analogues. J Am Chem Soc, 1999, 121(4): 775–779

    Article  CAS  Google Scholar 

  16. Son J H, Choi H, Kwon Y U. Porous crystal formation from polyoxometalate building blocks: Single-crystal structure of [AlO4Al12(OH)12(H2O)24][Al(OH)6Mo6O18]2((OH)·29.5H2O. J Am Chem Soc, 2000, 122: 7432–7433

    Article  CAS  Google Scholar 

  17. Zheng S T, Zheng L, Yang G Y. [{Zn(enMe)2}2(enMe)2{Zn2As8V12O40(H2O)}]·4H2O: A hybrid molecular material based on covalently linked inorganic Zn-As-V clusters and transition metal complexes via Me ligands. Eur J Inorg Chem, 2004, 2004–2007

  18. Zheng S T, Zheng L, Yang G Y. Hydrothermal sytheses and crystal structures of tow novel, hybrid materials based on secondary transition-metal-incorporated polyoxovanadate cluster backbones: [Cd(dien)2]2[(dien)CdAs8V13O41(H2O)]·4H2O and [Cd(dien)2] [(en)2Cd2As8V12O40]. Inorg Chem, 2005, 44: 2426–2430

    Article  CAS  Google Scholar 

  19. Xu Y, Xu J Q, Zhang K L, et al. Keggin unit supported transition metal complexes: Hydrothermal synthesis and characterization of [Ni(2,2′-bipy)3]1.5[PW12O40Ni(2,2′-bipy)2(H2O)]·0.5H2O and [Co(1,10′-phen)3]1.5[PMo12O40Co(1,10′-phen)2(H2O)]·0.5H2O. Chem Commun, 2000, 153–154

  20. Wang J P, Wang Z L, Niu J Y. Hydrothermal synthesis and structure characterization of a Keggin tungstocobaltate [Co(2,2′-bpy)3]2H2[CoW12O40]·9.5H2O. Polyhedron, 2004, 23: 773–777

    Article  Google Scholar 

  21. Wang J P, Wu Q, Niu J Y. A novel organic-inorganic complex: Synthesis and crystal structure of [Ca(DMSO)5(H2O)]SiMo12O40. Chin Chem Lett, 2002, 13: 915–918

    CAS  Google Scholar 

  22. Wang J P, Wu Q, Niu J Y. A novel one-dimensional organic-inorganic polymer: Synthesis and crystal structure of: {Ca(DMF)5}2SiMo12O40]n, Sci China Ser B-Chem, 2002, 45(6): 647–654

    Article  Google Scholar 

  23. Wang J P, Wei M L, Niu J Y. 1D-polyoxometalate-based composite compounds-Design, synthesis, crystal structures and properties of [{Ln(NMP)6}(PMo12O40)]n(Ln = La, Ce, Pr; NMP = N-methyl-2-pyrrolidone). Eur J Inor Chem, 2003, 48: 1–12

    Google Scholar 

  24. Wang J P, Wang Z L, Niu J Y. Hydrothermal synthesis and structure characterization of a-Keggin unit supported zinc-bipyridyl complex [Zn(2,2′-bpy)3]2[ZnW12O40Zn(2,2′-bpy)2]·H2O. Inorg Chem Commu, 2003, 6: 1272–1274

    Article  Google Scholar 

  25. Niu J Y, Wei M L, Wang J P. A novel 1D polyoxometallate-based coordination polymer [{Pr(DMSO)6(H2O)}(PMo12O40)·CH3CN]n, J Mol Struct, 2004, 689: 147–152

    Article  CAS  Google Scholar 

  26. Wang J P, Duan X Y, Niu J Y. Synthesis and crystal structure of a 1D double-chain polyoxometalate-based complex {[Ba(DMSO)3(H2O)3][C5H6N]PW12O40·DMSO·2H2O}n. J Mol Struct, 2004, 692: 17–21

    Article  CAS  Google Scholar 

  27. Wang J P, Wu Q, Niu J Y. Synthesis, crystal structure and properties of [Zn(DMF)6]H2SiW12O40·(CH3)NH. J Inorg Chem (in Chinese), 2002, 18: 957–960

    CAS  Google Scholar 

  28. Niu J Y, Han Q X, Wang J P. A novel Keggin units-supported complex: Synthesis, characterization and crystal structure of [(CH3)2NH2]6[Cu(DMF)4(GeW12O40)2]·2DMF. J Coord Chem, 2003, 56: 523–530

    Article  CAS  Google Scholar 

  29. Zhang H, Duan L, Lan Y. Synthesis, crystal structure, and photochromism of novel two-dimensional supramolecular networks based on Keggin-type polyoxoanion and lanthanide coordination cations. Inorg Chem, 2003, 42(24): 8053–8058

    Article  CAS  Google Scholar 

  30. Dolbecq A, Mialane P, Lisnard L, et al. Hybrid organic-inorganic 1D and 2D frameworks with ɛ-Keggin polyoxomolybdate as building block. Chem Eur J, 2003, 9: 2914–2920

    Article  CAS  Google Scholar 

  31. Niu J Y, Wu Q, Wang J P. 1D and 2D polyoxometalate-based composite compounds. Synthesis and crystal structure of [{Ba(DMSO)5(H2O)}2(SiMo12O40)] and [{Ba(DMSO)3(H2O)3} {B+a(DMSO)5(H2O)}(GeMo12O40)]. J Chem Soc Dalton Trans, 2002, 2512-2516

  32. Li J, Qi Y F, et al. Synthesis and anticancer-activity of 12-borotungstic acid 5-fluorine uracil salt. Chem J Chin Uni(in Chinese), 2004, 25: 1010–1012

    CAS  Google Scholar 

  33. Liu H Z, Sun W L, Yue B, et al. Synthesis and characterization of the germanium and boron-centered polytungstoruthenate. Chin J Inorg Chem(in Chinese), 1997, 13(3): 251–257

    CAS  Google Scholar 

  34. Wu Y P. The synthesis α-boron Wolfram heteropoly-acid outer salts and the study of its property. Journal of Jinzhou Medicine(in Chinese), 1998, 19(5):10–13

    CAS  Google Scholar 

  35. Fu G Y, Wang E B, Liu J F, et al. Preparations and properties of two heteropoly tunstoborate acids. Acta Chimica Sinica, 1985, 43: 949–954

    CAS  Google Scholar 

  36. Sheldrick G M. SHELX 97, Program for Crystal Structure Refinement. Göttingen: University of Göttingen, 1997

    Google Scholar 

  37. Wang E B, Wang G P, Huang R D. Keggin-type heteropolytungstate: UV spectrum and redox behavior. Chin Sci Bull (in Chinese), 1992, 37: 1195–1197

    Google Scholar 

  38. Li H J, Liu X F, Wang Y J, et al. Introduction for Nine Hundred and Ninety Nine Kinds of Chemical Products(in Chinese). Beijng: Metallurgical Industry Press, 1983. 405

    Google Scholar 

  39. Niu J Y, Wang J P. Introduction of Heteropoly Compound(in Chinese). Kaifeng: Publishing of Henan, 2000. 169

    Google Scholar 

  40. Wang J. Analytical Electrochemistry. New York: Wiley-VCH, 1994

    Google Scholar 

  41. Brett C M A, Brett A M O. Electrochemistry Principles, Methods and Applications. Oxford: Oxford University Press, 1993

    Google Scholar 

  42. Han Z G, Zhao Y L, Peng J, et al. The electrochemical behavior of Keggin polyoxometalate modified by tricyclic, aromatic entity. Electroanalysis, 2005, 17: 1097–1102

    Article  CAS  Google Scholar 

  43. Wang J P, Zhao J W, Niu J Y. A novel 1D zigzag chain organic-inorganic polymer with Dawson-type polyoxometalates as building blocks: Synthesis and crystal structure of H1.5[Sm(H2O)8]0.5[Sm(DMF)6(H2O)(α-P2W18O62)]·DMF·3H2O. J Mol Struct, 2004, 697: 191–198

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Molecular and Crystal Engineering, Institute of Chemistry and Chemical Engineering, Henan University, Kaifeng, 475001, China

    Wang Jingping, Li Jie & Niu Jingyang

Authors
  1. Wang Jingping
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Li Jie
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Niu Jingyang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Niu Jingyang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Wang, J., Li, J. & Niu, J. Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks. SCI CHINA SER B 49, 437–444 (2006). https://doi.org/10.1007/s11426-006-2014-9

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-006-2014-9

Keywords

Search

Navigation