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Organometallic Derivatives of Polyphosphazenes as Precursors for Metallic Nanostructured Materials

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Co-polyphosphazenes containing anchored organometallic fragments are useful precursors for nanostructured metallic materials. Pyrolysis in air at 800°C yields metallic nanoparticles of the type, M°/M x O y /M z (P x O y )/P4O7, depending on the metal used; i.e., M° when the metal is a noble metal, metal oxide when the metal is Cr, W and Ru, metallic pyrophosphate when M = Mn and Fe. The organic spacer of the polyphosphazene influences strongly the morphology of the pyrolytic product. The mechanism of formation of the nanostructured materials involves carbonization of the organic matter, which produces holes where the nanoparticles are grown. Reaction of the phosphorus polymeric chain with O2 yield phosphorus oxide units, which act as a P4O7 matrix to stabilize the nanoparticles and/or P x O −n y for the formation of metallic pyrophosphates. The method appears to be a general and versatile new route to metallic nanostructured materials.

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References

  1. (a) D. O’Hare and D. W. Bruce. Inorganic Materials (John Wiley & Sons, Chichester UK, 1992). (b) N. J. Coville and L. Cheng, J. Organomet. Chem. 571, 149 (1998). (c) P. J. Pickup. J. Mater. Chem. 9, 1641 (1999). (d) F. Ciardelli, E. Tsuchida, and D. Wohrle, Macromolecule–Metal Complexes (Springer, Berlin, 1996). (e) C. U. Pittman Jr, C. E. Carraher, M. Zeldin, J. E. Sheats, and B. M. Culbertson, Metal-containing Polymeric Material (Plenum, New York, 1996). (f) P. Wisian-Neilson, H. R. Allcock and K. J. Wynne, Inorganic and Organometallic Polymers II; Advanced Material and Intermediates (ACS Sym. Ser. 572, 1994).

  2. (a) P. Nguyen, P. Gomez-Elipe, and I. Manners, Chem. Rev. 99, 1515 (1999). (b) I. Manners, J. Chem. Commun. 857 (1999). (c) R. P. Kingsborough and T. M. Swager, Progr. Inorg. Chem. 48, 123 (1999).

  3. (a) H. R. Allcock, Adv. Mater. 6, 106 (1994). (b) I. Manners, Angew. Chem. Int. Ed. Engl. 35, 1602 (1996).

  4. (a) M. Gleria, R. De Jaeger (Eds), Phosphazenes: A World Wide Insight (Nova Science Publishers, New York, 2004). (b) H. R. Allcock, Chemistry and Applications of Polyphosphazenes (John Wiley & Sons, Hobokan, New York, 2003).

  5. (a) A. S. Edelstein and R. C. Cammarata, Nanomaterials: Synthesis Properties and Applications, (J. W. Arrowsmith Ltd., eds. Bristol, 2000). (b) K. J. Klabunde, Nanoscale Materials in Chemistry (Wiley-Interscience, New York, 2001).

  6. (a) J. Grunes, J. Gabor, and A. Somorjai, Chem. Commun. 2257 (2003). (b) A. T. Bell, Science 299, 1688 (2003).

  7. Ginzburg M., MacLachlan M. J., MingYang S., Coombs N., Coyle T. W., Praju N., Greendan J. E., Herber R. H., Ozin G .A., Manners I. (2002) J. Am. Chem. Soc. 124: 2625

    Article  CAS  Google Scholar 

  8. Petersen R., Foucher D. A., Tang B., Lough A., Praju N., Greedan J. E., Herber R. H., Manners I. (1995) Chem. Mater. 7: 2045

    Article  CAS  Google Scholar 

  9. Terenish T., Hasegawa S., Shimizu T., Miyake M. (2001) Adv. Mater. 13: 1699

    Article  Google Scholar 

  10. Shimizu T., Teranishi T., Hasegawa S., Miyake M. (2003) J. Phys. Chem. 107: 2719

    CAS  Google Scholar 

  11. Qiu J., Jiang X., Zhu C., Shirai M., Jiang N. J. (2004) Angew. Chem. Int. Ed. 43: 2230

    Article  CAS  Google Scholar 

  12. Leite E. R., Carreño N. L.V. , Lango E., F. M. Pontes, Barison A., Ferreiro A. G., Maniette Y., Varela J. A. (2002) Chem. Mater. 14: 3722

    Article  CAS  Google Scholar 

  13. Boxall D. L., Kenik E. A., Lukehart C. M. (2002) Chem. Mater. 14: 1715

    Article  CAS  Google Scholar 

  14. Roucoux A., Schulz J., Patin H. (2002) Chem. Rev. 102: 3757

    Article  CAS  Google Scholar 

  15. C. Díaz and M. L. Valenzuela, in Horizons in Polymer Research, R. B. Bregg, ed. (Nova Science Publishers, 2005), Chapter 6.

  16. Díaz C., Castillo P. (2002) J. Inorg. Organomet. Polym. 11: 183

    Article  Google Scholar 

  17. Carriedo G. A., García Alonso F. J., Gonzalez P., Gomez-Elipe P. (1999) Polyhedron 18: 2853

    Article  CAS  Google Scholar 

  18. C. Díaz, Castillo P., Carriedo G. A., Gómez-Elipe P., García Alonso F. J. (2002) Macromol. Phys. Chem. 203: 1912

    Article  Google Scholar 

  19. Carriedo G. A., García Alonso F. J., Gómez-Elipe P., Díaz C., Yutronic N. (2003) J. Chilean Chem. Soc. 48: 25

    CAS  Google Scholar 

  20. Díaz C., Castillo P. (2003) Polym Bull. 50: 123

    Article  Google Scholar 

  21. Díaz C., Valenzuela M. L., Barbosa M. (2004) Mater. Res. Bull. 39: 9

    Article  Google Scholar 

  22. Carriedo G.A., García Alonso F.J., García Álvarez J.L., Díaz C., Yutronic N. (2000) Polyhedron 21: 2587

    Article  Google Scholar 

  23. Olshavsky M. A., Allcock H. R. (1997) Chem. Mater. 9: 1367

    Article  CAS  Google Scholar 

  24. Walker C. H., St. John J. V., Wisian-Neilson P. (2001) J. Am. Chem. Soc. 123: 3846

    Article  CAS  Google Scholar 

  25. Jung J., Kmecko T., Claypool C. L., Zhang H., Wisian-Neilson P. (2005) Macromolecules 38: 2122

    Article  CAS  Google Scholar 

  26. Carriedo G. A., García Alonso F. J., Díaz C., Valenzuela M. L. (2006) Polyhedron 25: 105

    Article  CAS  Google Scholar 

  27. Díaz C., Castillo P., Valenzuela M. L. (2006) J. Cluster Sci. 16: 515

    Article  Google Scholar 

  28. Diaz C., Valenzuela M. L. (2005) Macromolecules 39: 103

    Article  Google Scholar 

  29. Carriedo G. A., García Alonso F. J., García Álvarez J. L., Díaz C., Yutronic N. (2000) Polyhedron 21: 2579

    Article  Google Scholar 

  30. Diaz C., Valenzuela M. L. (2006) J. Inorg. Organomet. Polym. 16: 123

    Article  CAS  Google Scholar 

  31. C. Díaz, M. L. Valenzuela, E. Spodine, Y. Moreno, and O. Peña, submitted

  32. M. Valle, J. López-Ruiz, J. M. Badia, and P. Adeva, Microscopia Electrónica de Barrido y Microanálisis por Rayos X, Chapter 23. (Rueda, Madrid, 1996).

  33. Cotton F. A., Mague J. T. (1966) Inorg. Chem. 5: 317

    Article  CAS  Google Scholar 

  34. C. Díaz, F. J. García-Alonso, G. Carriedo, and M. L. Valenzuela, Unpublished results.

  35. C. Díaz, M. L. Valenzuela, and N.Yutronic. J. Inorg. Organomet. Polym. Mater. (2006). In press.

  36. Akamatsu K., Kawamura T., Nabira H., Deki S., Strunskus T., Faupel F. (2002) J. Mater. Chem. 12: 3610

    Article  CAS  Google Scholar 

  37. Nath S., Praharay S., Panigrahi S., Kumar Ghosh S., Kundu S., Basu S., T. Pol. (2005) Langmuir 21:10405

    Article  CAS  Google Scholar 

  38. Yu H., Chen M., Rice P. M., Wang S. X., Whiteand R. L., Sun S. (2005) Nano. Lett. 5: 379

    Article  CAS  Google Scholar 

  39. C. Diaz, M. L. Valenzuela, A. Laguna, I. Jimenez, Unpublished results

  40. C. Diaz, M. L. Valenzuela, D. Abizanda, I. Jimenez, and A. Laguna. J. Inorg. Organomet. Polym. Mater. (2006) In Press.

  41. Dachille F., Dent-Glasser L. (1959) Acta Crytallogr. 12: 280

    Article  Google Scholar 

  42. Allcock H. R., Brennan D. J. (1998) J. Organomet. Chem. 341: 231

    Article  Google Scholar 

  43. Allcock H. R., Brennan D. J., Dunn B. S. (1989) Macromolecules. 22: 1534

    Article  CAS  Google Scholar 

  44. Allcock H. R., Coggio W. D., Archibald R. S., Brennan D. J. (1989) Macromolecules. 22: 3571

    Article  CAS  Google Scholar 

  45. Allcock H. R., Coggio W. D. (1990) Macromolecules. 23: 1629

    Google Scholar 

  46. Allcock H. R., Kuhercik S. E., Nelson C. J. (1996) Macromolecules 29: 3686

    Article  CAS  Google Scholar 

  47. Allcock H.R., Kuhercik S.E. (1995) J. Inorg. Organomet. Polym. 5: 307

    Article  CAS  Google Scholar 

  48. Allcock H. R., Kuhercik S. E. (1996) J. Inorg. Organomet. Polym. 6: 1

    Article  CAS  Google Scholar 

  49. G. A. Carriedo, F. J. García Alonso, A. Presa, C. Diaz, M. L.Valenzuela, Unpublished results

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Acknowledgments

We acknowledge with thanks the financial support under FONDECYT Project 1030515.

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Authors and Affiliations

  1. Departamento de Química, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Santiago, Chile

    C. Díaz & M. L. Valenzuela

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  1. C. Díaz
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  2. M. L. Valenzuela
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Correspondence to C. Díaz.

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Dedicated to Professor Harry Allcock for his pioneering and persevering work on Polyphosphazene and their projection in another field as materials and recently nanomaterials.

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Díaz, C., Valenzuela, M.L. Organometallic Derivatives of Polyphosphazenes as Precursors for Metallic Nanostructured Materials. J Inorg Organomet Polym 16, 419–435 (2006). https://doi.org/10.1007/s10904-006-9058-3

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