Skip to main content

Prospects for Rational Assembly of Composite Polyoxometalates

  • Chapter
Polyoxometalate Chemistry for Nano-Composite Design

Conclusions

The directed synthesis of large inorganic polyoxometalates with specific structural and stereochemical features remains an elusive but not unattainable goal. We have shown that opportunities exist for straightforward assembly of stable or metastable polyoxometalate subunits using principles of both coordination chemistry and organic synthesis. Among the many advantages offered by such synthetic approaches is the generation of chiral structures for molecular recognition and catalytic selectivity that we are currently pursuing.

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

Access this chapter

eBook
USD 16.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 16.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. A. Müller, E. Krickemeyer, J. Meyer, H. Bögge, F. Peters, W. Plass, E. Diemann, S. Dillinger, F. Nonnenbruch, M. Randerath, and C. Menke [Mo 154 (NO) 14 O 420 (OH) 28 (H 2 O) 70 ] (25±5) −: a water-soluble big wheel with more than 700 atoms and a relative molecular mass of about 24 000, Angew. Chem. Int. Ed. Engl. 34:2122 (1995); (b) K. Wassermann, M.H. Dickman, and M.T. Pope, Self-assembly of supramolecular polyoxometalates. The compact, water-soluble heteropolytungstate anion [As III 12 Ce III 16 (H 2 O) 36 W 148 O 524 ] 76−, Angew. Chem. Int. Ed. Engl. 36:1445 (1997); (c) A. Müller, E. Krickemeyer, H. Bögge, M. Schmidtmann, and F. Peters, Organizational forms of matter: an inorganic superfullerene and keplerate based on molybdenum oxide, Angew. Chem., Int. Ed. Engl. 37:3360 (1998).

    Article  Google Scholar 

  2. A. Müller, F. Peters, M.T. Pope, and D. Gatteschi, Polyoxometalates: very large clusters-nanoscale magnets, Chem. Rev. 98:239 (1998); (b) J. M Clemente-Juan and E. Coronado, Magnetic clusters from polyoxometalate complexes, Coord. Chem. Rev. 193–195:361 (1999)

    Article  Google Scholar 

  3. C. M. Flynn, Jr. and G. D. Stuckey, Crystal structure of sodium 12-niobomanganate(IV), Na 12 [MnNb 12 O 38 ].50H 2 O, Inorg. Chem. 8:335 (1969)

    Article  CAS  Google Scholar 

  4. C. M. Tourné, G. Tourné, and M. C. Brianso, Cesium uranium germanium tungstate, Cs 12 [U(GeW 11 O 39 ) 2 ]·13–14 H 2 O, Acta Crystallogr., Sect B 36:2012 (1980)

    Article  Google Scholar 

  5. F. Robert, M. Leyrie, A Tézé, G. Hervé, and Y. Jeannin, Crystal structure of ammonium dicobalto(II)-40-tungstotetraarsenate(III). Allosteric effects in the ligand, Inorg. Chem. 19:1746 (1980); (b) K. Wassermann and M.T. Pope, Large cluster formation through multiple substitution with lanthanide cations (La, Ce, Sm, Eu and Gd) of the polyoxoanion [ B-α(AsO 3 W 9 O 30 ) 4 (WO 2 ) 4 ] 28−. Synthesis and structural characterization, Inorg. Chem. 40:2763 (2001)

    Article  CAS  Google Scholar 

  6. A. Tézé, M. Michelon, and G. Hervé, Syntheses and structures of the tungstoborate anions, Inorg. Chem. 36:505 (1997)

    Article  Google Scholar 

  7. J. Fischer, L. Ricard, and R. Weiss, The structure of the heteropolytungstate (NH 4 ) 17 Na[NaSb 9 W 21 O 86 ] 14 H 2 O An inorganic cryptate, J. Am. Chem. Soc. 98:3050 (1976); (b) M. Michelon, G. Hervé, M. Leyrie, Synthesis and chemical behavior of the inorganic cryptates. Ammonium, alkali, and alkaline earth antimony tungstates [MSb 9 W 21 O 86 I(19−n)− Mn +=Na +, K +, NH 4 +, Ca 2+, Sr 2+, Inorg. Nucl. Chem. 42:1583 (1980)

    Article  CAS  Google Scholar 

  8. R.D. Peacock and T.J.R. Weakley, Heteropolytungstate complexes of the lanthanide elements. Part 1. Preparation and reactions, J. Chem. Soc. (A) 1836 (1971)

    Google Scholar 

  9. V.N. Molchanov, L.P Kazanskii, E.A. Torchenkova, and V.I. Simonov, Crystal structure of K 16 [Ce(P 2 W 17 O 61 ) 2 ]·n H 2 O (n=50) Sov. Phys. Crystallog. (Engl. Transl.) 24:96 (1979)

    Google Scholar 

  10. Q.H. Luo, R.C. Howell, M. Dankova, J. Bartis, C.W. Williams, W. DeW. Horrocks, Jr., V.G. Young, Jr., A.L. Rheingold, L.C. Francesconi, and M.R. Antonio, Coordination of rare-earth elements in complexes with monovacant Wells-Dawson polyoxoanions, Inorg. Chem. 40:1894 (2001); (b) A. Ostuni, R.E. Bachman, A.K. Jameson, and M.T.Pope, Diastereomers of the Peacock-Weakley heteropolytungstates, [Mn +(α m-P 2 W 17 O 61)2]20·n (M=An IV, Ln III, m=1,2). Syn-and anticonformations of the polytungstate ligands. Structures of the α1,α1, α1α2 and α2α2 complexes, In preparation

    Article  CAS  Google Scholar 

  11. A.B. Yusov and A.M. Fedoseev, Effect of water molecules on photolumincscence of curium(III) and rare-earth metals(III) in complexes with polytungstate ligands, Zh. Prikl. Spektrosk. 49:929 (1988); Chem. Abstr. 111:67023p (1989); (b) J. Bartis, M. Dankova, J. J. Lessmann, Q.H. Luo, W. DeW. Horrocks, Jr., and L.C. Francesconi, Lanthanide complexes of the α−1 isomer of the [P 2 W 17 O 61 ] 10− heteropolytungstate: Preparation, stoichiometry, and structural characterization by 183W and 31P NMR spectroscopy and europium(III) luminescence spectroscopy, Inorg. Chem. 38:1042 (1999)

    CAS  Google Scholar 

  12. M. Sadakane, M.H. Dickman, and M.T. Pope, Controlled assembly of polyoxometalate chains from lacunary building blocks and lanthanide-cation linkers, Angew. Chem. Int. Ed. Engl. 39:2914 (2000); (b) M. Sadakane, M.H. Dickman, and M.T. Pope, Chiral polyoxotungstates. 1. Stereoselective interaction of amino acids with enantiomers of [Ce III (α 1-P 2 W 17 O 61 )(H 2 O 2]7, The structure of DL-[Ce 2 (H 2 O) 8 (P 2 W 17 O 61 ) 2 ] 14−, Inorg. Chem. 40:2715 (2001)

    Article  CAS  Google Scholar 

  13. J.P. Ciabrini, and R. Contant, Mixed heteropolyanions. Synthesis and formation constants of cerium(III) and cerium(IV) complexes with lacunary tungstophosphates,, J. Chem. Res, (S), 391 (1993); (M), 2720 (1993)

    Google Scholar 

  14. A. Ostuni, Lanthanide and actinide complexes of the lacunary Wells-Dawson anions: synthesis, structure and spectroscopy, M.S. Thesis, Georgetown University, 1998

    Google Scholar 

  15. J. Iball, J.N. Low, and T.J.R. Weakley, Heteropolytungstate complexes of the lanthanoid elements. III. Crystal structure of sodium decatungstocerate(IV) tricontahydrate,, J. Chem. Soc., Dalton Trans. 2021 (1974); (b) T. Ozeki and T. Yamase, Effect of lanthanide contraction on the structures of the decatungstolanthanoate anions in K 3 Na 4 H 2 [LnW 10 O 36 ]·nH 2 O (Ln=Pr, Nd, Sm, Gd, Tb, Dy) crystals, Acta Crystallogr., Sect. B 50:128 (1994)

    Google Scholar 

  16. T. Yamase, H. Naruke, and Y. Sasaki, Crystallographic characterization of the polyoxotungstate [Eu 3 (H 2 O) 3 (SbW 9 O 33 )(W 5 O 18 ) 3 ] 18− and energy transfer in its crystalline lattices, J. Chem, Soc., Dalton Trans. 1687 (1990); (b) H. Naruke, and T. Yamase, A novel-type mixed-ligand polyoxotungstolanthanoate, [Ln(BW 11 O 39 )(W 5 O 18 )] 12− (Ln=Ce 3+ and Eu 3+ ), Bull. Chem. Soc. Jpn. 73:375 (2000)

    Google Scholar 

  17. N. Belai, M. Sadakane, and M.T. Pope, Formation of unsymmetrical polyoxotungstates via transfer of polyoxometalate building blocks. NMR evidence supports the kinetic stability of the pentatungstate anion, [W 5 O 18 ] 6−, in aqueous solution, J. Am. Chem. Soc. 123:2087 (2001)

    Article  CAS  Google Scholar 

  18. L.C.W. Baker and J.S. Figgis, A new fundamental type of inorganic complex: hybrid between heteropoly and conventional coordination complexes. Possibilities for geometrical isomerisms in 11-, 12-, 17-, and 18-heteropoly derivatives, J. Am. Chem. Soc. 92:3794 (1970); (b) J. Park, M. Ko, and H. So, NMR spectra of 4,4’-bipyridyl, pyrazine, and ethylenediamine coordinated to undecatungstocobalto(III)silicate and-borate anions. Identification of 1:1 and dumbbell-shaped 1:2 complexes, Bull. Korean Chem. Soc, 14:759 (1993); (c) J.L. Samonte and M.T. Pope, Derivatization of polyoxotungstates in aqueous solution. Exploration of the kinetic stability of cobalt(II)-and cobalt(III) derivatives of lacunary anions with pyridine and pyridine-type ligands, Can. J. Chem.. In press

    Article  CAS  Google Scholar 

  19. G.S. Chorghade and M.T. Pope, Heteropolyanions as nucleophiles. I. Synthesis, characterization and and reactions of Keggin-and Dawson-Type tungstostannates(II), J. Am. Chem. Soc. 109:5234 (1987); (b) F. Xin and M.T. Pope, Polyoxometalate derivatives with multiple organic groups. 1. Synthesis and structures of tris(organotin) β-Keggin and α-Dawson tungstophosphates, Organometallics, 13:4881 (1994); (c) F. Xin, M.T. Pope, G.J. Long, and U. Russo, Polyoxometalate derivatives with multiple organic groups. 2. Synthesis and structures of tris(organotin) α,β-Keggin tungstosilicates, Inorg. Chem., 35:1207 (1996); (d) F. Xin and M.T. Pope, Polyoxometalate derivatives with multiple organic groups. 3. Synthesis and structure of bis(phenyltin)bis(decatungstosilicate), [(PhSnOH 2 ) 2 (γ-SiW 10 O 36 ) 2 ] 10−, Inorg.Chem., 35:5693 (1996); (e) G. Sazani, M.H. Dickman, and M.T. Pope, Organotin derivatives of α[X III W 9 O 33 ] 9− (X=As, Sb) heteropolytungstates. Solution and solid state characterization of [{(C 6 H 5 Sn) 2 O} 2 H(AsW 9 O 33 ) 2 ] 9− and [(C 6 H 5 Sn) 3 Na 3 (SbW 9 O 33 ) 2 ] 6−, Inorg. Chem. 39:939 (2000)

    Article  Google Scholar 

  20. G. Sazani, Synthesis and Characterization of Novel Functionalized Organotin and Organogermanium Derivatives of Heteropolyanions, Ph.D. Thesis, Georgetown University, 1999

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2002 Kluwer Academic Publishers

About this chapter

Cite this chapter

Belai, N. et al. (2002). Prospects for Rational Assembly of Composite Polyoxometalates. In: Yamase, T., Pope, M.T. (eds) Polyoxometalate Chemistry for Nano-Composite Design. Nanostructure Science and Technology. Springer, Boston, MA. https://doi.org/10.1007/0-306-47933-8_2

Download citation

  • DOI: https://doi.org/10.1007/0-306-47933-8_2

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-0-306-47359-3

  • Online ISBN: 978-0-306-47933-5

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics