Synthesis and electrochemistry of new tetrathiafulvalene (TTF) dendrimers:X-ray crystal structure of a tetrafunctionalised TTF core unit

Abstract

A new synthetic approach to tetrathiafulvalene (TTF) dendrimers is reported. Tetrakis(4-chloromethylbenzylthio)tetrathiafulvalene7 is a functionalised core unit which reacts with four equivalents of the thiolate ion generated from compound 16 to afford the trisdeca-TTF derivative 3. Compound 3 is a shelf-stable solid which has been characterised by elemental analysis, MALDI-TOF mass spectrometry, ¹H NMR spectroscopy and solution electrochemistry. Thin layer cyclic voltammetry studies on pentakis-TTF and trisdeca-TTF derivatives 11 and 3 in dichloromethane solution in the presence of 2,3-dichloronaphthoquinone as an internal reference, show that all the TTF units undergo two single-electron oxidations. The single crystal X-ray structure of compound 7 is reported: the molecules have crystallographic C_i symmetry and form chair-like stacks parallel to the crystallographic y axis.

References

1. G. M. Whitesides, J. P. Mathias and C. T. Seto, Science, 1991, 254, 1312.
2. Reviews: (a) G. R. Newkome, C. N. Moorefield and G. R. Baker, Aldrichim. Acta, 1992, 25, 31; (b) D. A. Tomalia and H. D. Durst, in Supramolecular Chemistry I—Directed Synthesis and Molecular Recognition, ed. E. Weber, Springer-Verlag, Berlin, 1993, 193; (c) C. N. Moorefield and G. R. Newkome, in Advances in Dendritic Macromolecules, ed. G. R. Newkome, JAI Press, London, 1994, vol. 1, p. 1; (d) J. M. J. Fréchet, Science, 1994, 263, 1710; (e) D. A. Tomalia, Adv. Mater., 1994, 6, 529; (f) G. R. Newkome and C. N. Moorefield, in Mesomolecules: From Molecules to Materials, ed. G. D. Mendenhall, A. Greenberg and J. F. Liebman, Chapman and Hall, New York, 1995, p. 27; (g) N. Ardoin and D. Astruc, Bull. Soc. Chim. Fr., 1995, 132, 875.
3. P. Hodge, Nature, 1993, 362, 18.
4. T. Nagasaki, O. Kimura, M. Ukon, S. Arimori, I. Hamachi and S. Shinkai, J. Chem. Soc., Perkin Trans 1, 1994, 75.
5. (a) G. R. Newkome, X. Liu and C. D. Weis, Tetrahedron: Asymmetry, 1991, 2, 957; (b) J. F. G. A. Jansen, H. W. I. Peerlings, E. M. M. de Brabander-Van den Berg and E. W. Meijer, Angew. Chem., Int. Ed. Engl., 1995, 34, 1206.
6. S. Campagne, G. Denti, S. Serroni, A. Juris, M. Venturi, V. Ricevuto and V. Balzani, Chem. Eur. J., 1995, 1, 211.
7. (a) V. Percec, P. Chu and M. Kawasumi, Macromolecules, 1994, 27, 4441; (b) K. Lorenz, D. Hölter, B. Stühn, R. Mülhaupt and H. Frey, Adv. Mater., 1996, 8, 414.
8. For reviews which emphasise the functional properties of dendrimers see: (a) J. Issberner, R. Moors and F. Vögtle, Angew. Chem., Int. Ed. Engl., 1994, 33, 2413; (b) R. Moors and F. Vögtle, in Advances in Dendritic Macromolecules, ed. G. R. Newkome, JAI Press, London, 1996, vol. 2, p. 41.
9. For an article summarising recent publications on functional dendrimers, see R. Dagani, Chem. Eng. News, June 3, 1996, 30.
10. For a review of redox-active dendrimers, see M. R. Bryce and W. Devonport, in Advances in Dendritic Macromolecules, ed. G. R. Newkome, JAI Press, London, 1996, vol. 3, p. 115.
11. (a) P. J. Dandliker, F. Diederich, M. Gross, C. B. Knobler, A. Louati and E. M. Sanford, Angew. Chem., Int. Ed. Engl., 1993, 33, 1739; (b) P. J. Dandliker, F. Diederich, J.-P. Gisselbrecht, A. Louati and M. Gross, Angew. Chem., Int. Ed. Engl., 1994, 34, 2725.
12. M. R. Bryce, W. Devonport and A. J. Moore, Angew. Chem., Int. Edn. Engl., 1994, 33, 1761.
13. (a) J. R. Ferraro and J. M. Williams, Introduction to Synthetic Electrical Conductors, Academic Press, London, 1987; (b) M. R. Bryce, Chem. Soc. Rev., 1991, 20, 355; (c) A. E. Underhill, J. Mater. Chem., 1992, 2, 1; (d) J. Mater. Chem., Special Issue on Molecular Conductors, 1995, 5, 1469.
14. Review: M. Adam and K. Müllen, Adv. Mater., 1994, 6, 439.
15. (a) M. Jørgensen, K. A. Lerstrup and K. Bechgaard, J. Org. Chem., 1991, 56, 5684; (b) M. R. Bryce, G. J. Marshallsay and A. J. Moore, J. Org. Chem., 1992, 57, 4859; (c) I. V. Sudmale, G. V. Tormos, V. Yu. Khodorkovsky, A. S. Edzina, O. J. Neilands and M. P. Cava, J. Org. Chem., 1993, 58, 1355; (d) L. M. Goldenberg, V. Yu. Khodorkovsky, J. Y. Becker, M. R. Bryce and M. C. Petty, J. Mater. Chem., 1995, 5, 191; (e) J. Y. Becher, J. Bernstein, A. Ellern, H. Gershenman and V. Khodorkovsky, J. Mater. Chem., 1995, 5, 1557; (f) Review: T. Otsubo, Y. Aso and K. Takimiya, Adv. Mater., 1996, 8, 203.
16. (a) F. Gerson, A. Lamprecht and M. Fourmigué, J. Chem. Soc., Perkin Trans. 2, 1996, 1409; (b) M. Adam, E. Fanghänel, K. Müllen, Y.-J. Shen and R. Wegner, Synth. Met., 1994, 66, 275; (c) R. P. Parg, J. D. Kilburn, M. C. Petty, C. Pearson and T. G. Ryan, J. Mater. Chem., 1995, 5, 1609; (d) Z.-T. Li and J. Becher, Chem. Commun, 1996, 639.
17. (a) G. J. Marshallsay, T. K. Hansen, A. J. Moore, M. R. Bryce and J. Becher, Synthesis, 1994, 926; (b) J. Lau, O. Simonsen and J. Becher, Synthesis, 1995, 521.
18. M. A. Blower, M. R. Bryce and W. Devonport, Adv. Mater., 1996, 8, 63.
19. S. Frenzel, S. Arndt, R. Ma. Gregoroius and K. Müllen, J. Mater. Chem., 1995, 5, 1529.
20. M. R. Bryce and W. Devonport, Synth. Met., 1996, 76, 305.
21. W. Devonport, Ph.D. Thesis, University of Durham, 1995.
22. (a) G. Steimecke, H.-J. Sieler, R. Kirmse and E. Hoyer, Phosphorus Sulfur, 1979, 7, 49; (b) Review: N. Svenstrup and J. Becher, Synthesis, 1995, 215.
23. A. Krief, Tetrahedron, 1986, 42, 1209.
24. (a) N. Svenstrup, K. M. Rasmussen, T. K. Hansen and J. Becher, Synthesis, 1994, 809; (b) J. Becher, J. Lau, P. Leriche, P. Mørk and N. Svenstrup, J. Chem. Soc., Chem. Commun., 1994, 2715.
25. (a) D. L. Lichtenberger, R. L. Johnston, K. Hinkelmann, T. Suzuki and F. Wudl, J. Am. Chem. Soc., 1990, 112, 3302 and references cited therein.
26. A. J. Moore and M. R. Bryce, J. Chem. Soc., Chem. Commun., 1991, 1638.
27. (a) A. T. Hubbard and F. C. Anson, in Electroanalytical Chemistry, ed. A. J. Bard, Marcel Dekker, New York, 1970, vol. 4, pp. 129–210; (b) R. Carlier and J. Simonet, Bull. Soc. Chim. Fr., 1988, 831.
28. (a) R. Carlier, P. Frere, M. Sallé, J. Roncali, M. Jubault, A. Tallec and A. Gorgues, Adv. Mater., 1993, 5, 445; (b) P. Frere, R. Carlier, K. Boubekeur, A. Gorgues, J. Roncali, A. Tallec, M. Jubault and P. Batail, J. Chem. Soc., Chem. Commun., 1994, 2071.
29. C. M. Casaco, I. Cuadrado, M. Morán and J. Losada, J. Chem. Soc., Chem. Commun., 1994, 2575.
30. 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.
31. D. Astruc, Electron Transfer and Radical Processes in Transition Metal Chemistry, VCH, New York, 1995, ch. 2.
32. (a) J.-L. Fillaut, J. Linars and D. Astruc, Angew. Chem., Int. Ed. Engl., 1994, 33, 2460; (b) P. Jutzi, C. Batz, B. Neumann and H.-G. Stammler, Angew. Chem., Int. Ed. Engl., 1996, 35, 2118.
33. (a) C. Nakano, K. Imaeda, T. Mori, Y. Maruyama, H. Inokuchi, N. Iwasawa and G. Saito, J. Mater. Chem., 1991, 1, 37; (b) A. S. Batsanov, N. Svenstrup, J. Lau, J. Becher, M. R. Bryce and J. A. K. Howard, J. Chem. Soc., Chem. Commun., 1995, 1201.
34. For a review of TTF derivatives in supramolecular chemistry, see T. Jørgensen, T. K. Hansen and J. Becher, Chem. Soc. Rev., 1994, 23, 41.
35. G. M. Sheldrick, SHELXTL, ver. 5/VMS, Siemens Analytical X-Ray Instruments Inc., Wisconsin, USA, 1995.