Organometallic ferrocenyl dendrimers: synthesis, characterization and redox properties

(Note: The full text of this document is currently only available in the PDF Version )

Ching-Fong Shu and Hsiu-Ming Shen


Abstract

A series of dendritic poly(aryl ether)s containing 3, 6, 12 and 24 ferrocene functionalities located exclusively at the peripheries of the dendritic structures have been synthesized using the stepwise convergent approach. The structures of these dendrimers have been characterized using1H and 13C NMR spectroscopy. Cyclic and normal pulse voltammetric studies indicate that the ferrocenyl moieties located on the outer surfaces of these dendrimers are non-interacting redox centres, are electrochemically equivalent, and are oxidizable at the same potential. The results of controlled-potential coulometric oxidation show that nearly all the ferrocene residues in the dendrimers are accessible to electron transfers in electrode reactions.


References

  1. P. D. Hale, J. Inagaki, H. I. Karan, Y. Okamoto and T. A. Stotheim, J. Am. Chem. Soc., 1989, 111, 3482 CrossRef CAS; M. E. Wright and M. S. Sigman, Macromolecules, 1992, 25, 6055 CrossRef CAS; A. Togni and G. Rihs, Organometallics, 1993, 12, 3368 CrossRef CAS.
  2. D. A. Tomalia, A. M. Naylor and W. A. Goddard, Angew. Chem., Int. Ed. Engl., 1990, 29, 138 CrossRef; H. Mekelburger, W. I. Jaworke and F. Vögtle, Angew. Chem., Int. Ed. Engl., 1992, 31, 1571 CrossRef; J. M. J. Fréchet, Science, 1994, 263, 1710 CrossRef CAS.
  3. D. A. Tomalia, H. Baker, J. R. Dewald, M. Hall, G. Kallos, S. Martin, J. Roeck, J. Ryder and P. Smith, Macromolecules, 1986, 19, 2466 CrossRef; G. R. Newkome, Z. Yao, G. R. Baker, V. K. Gupta, P. S. Russo and M. J. Saunders, J. Am. Chem. Soc., 1986, 108, 849 CrossRef CAS; G. R. Newkome, A. Nayak, R. K. Behara, C. N. Moorefield and G. R. Baker, J. Org. Chem., 1992, 57, 358 CrossRef CAS; H. Uchida, Y. Kabe, K. Yoshino, A. Kawamata, T. Tsumuraya and S. Masamune, J. Am. Chem. Soc., 1990, 112, 7077 CrossRef CAS.
  4. J. L. Fillaut and D. Astruc, J. Chem. Soc., Chem. Commun., 1993, 1320 RSC; F. Moulines, L. Djakovitch, R. Boese, B. Gloaguen, W. Thiel, J. L. Fillaut, M. H. Delville and D. Astruc, Angew. Chem., Int. Ed. Engl., 1993, 32, 1075 CrossRef; Y.-H. Liao and J. R. Moss, J. Chem. Soc., Chem. Commun., 1993, 1774 RSC; B. Alonso, I. Cuadrado, M. Moran and J. Losada, J. Chem. Soc., Chem. Commun., 1994, 2575 RSC; Y.-H. Liao and J. R. Moss, Organometallics, 1995, 14, 2130 CrossRef CAS; K. Lorenz, R. Muhaupt, H. Frey, U. Rapp and F. J. Mayer-Posner, Macromolecules, 1995, 28, 6657 CrossRef CAS.
  5. T. Nagasaki, M. Ukon, S. Arimori and S. Shinkai, J. Chem. Soc., Chem. Commun., 1992, 608 RSC; G. R. Newkome, F. Cardullo, E. C. Constable, C. N. Moorefield and A. M. W. C. Thompson, J. Chem. Soc., Chem. Commun., 1993, 925 RSC; S. Achar and R. J. Puddephatt, Angew. Chem., Int. Ed. Engl., 1994, 33, 847 CrossRef; G. R. Newkome, C. N. Moorefield, J. M. Keith, G. R. Baker and G. H. Escamilla, Angew. Chem., Int. Ed. Engl., 1994, 106, 701 CAS; S. Serroni, G. Denti, S. Campagna, A. Juris, M. Ciano and V. Balzani, Angew. Chem., Int. Ed. Engl., 1992, 104, 1540 CAS.
  6. R.-H. Jin, T. Aida and S. Inoue, J. Chem. Soc., Chem. Commun., 1993, 1260 RSC; C. J. Hawker, K. L. Wooley and J. M. J. Fréchet, J. Am. Chem. Soc., 1993, 115, 4375 CrossRef CAS; K. L. Wooley, C. J. Hawker, J. M. J. Frechet, F. Wudl, G. Srdanov, S. Shi, C. Li and M. Kao, J. Am. Chem. Soc., 1993, 115, 9836 CrossRef CAS; P. J. Dandliker, F. Diederich, J.-P. Gissebrecht, A. Louati and M. Gross, Angew. Chem., Int. Ed. Engl., 1995, 34, 2725 CrossRef CAS.
  7. C. Hawker and J. M. J. Fréchet, J. Am. Chem. Soc., 1990, 112, 7638 CrossRef CAS; K. L. Wooley, C. J. Hawker and J. M. J. Fréchet, J. Chem. Soc., Perkin Trans. 1, 1991, 1059 RSC; C. J. Hawker and J. M. J. Fréchet, J. Am. Chem. Soc., 1992, 114, 8405 CrossRef CAS.
  8. D. T. Sawyer and J. L. Roberts Jr., Experimental Electrochemistry for Chemists, Wiley, New York, 1979 Search PubMed.
  9. K. Schlogel, Monatsh. Chem., 1957, 88, 601 CrossRef CAS.
  10. C. G. Pitt, H. H. Seltzman, Y. Sayed, C. E. Twine Jr. and D. L. Willians, J. Org. Chem., 1979, 44, 677 CrossRef CAS.
  11. J. Hooz and S. S. H. Gilani, Can. J. Chem., 1968, 46, 86 CAS.
  12. E. Reimann, Chem. Ber., 1968, 102, 2887.
  13. J. B. Flanagan, S. Margel, A. J. Bard and F. C. Anson, J. Am. Chem. Soc., 1978, 100, 4248 CrossRef CAS.
  14. T. W. Smith, J. E. Kuder and D. Wychich, J. Polym. Sci., 1976, 15, 2433 Search PubMed.
  15. C. D'Silva, S. Afeworki, O. L. Parri, P. K. Baker and A. E. Underhill, J. Mater. Chem., 1992, 2, 225 RSC.
  16. J. B. Flangan, K. Takahashi and F. C. Anson, J. Electroanal. Chem., 1977, 85, 257 CrossRef.
  17. P. J. Dandliker, F. Diederich, M. Gross, C. B. Knobler, A. Louati and E. M. Sanford, Angew. Chem., Int. Ed. Engl., 1994, 33, 1739 CrossRef.
Click here to see how this site uses Cookies. View our privacy policy here.