The synthesis, redox properties and X-ray crystal structures of two new tetrathiafulvalene-thiophene donors

Abstract

The functionalisation of tetrathiafulvalene with thiophene units is reported via the synthesis of two multiredox compounds 4 and 5. The two molecules represent a fused structure (4) and a TTF-thiophene system directly linked by a single bond (5); both compounds are endowed with ' 2,5-positions within the thiophene ring, making them accessible to polymerisation reactions. The solution electrochemistry of 4 and 5 reveals the redox properties of the two components: a three-stage oxidation process is seen in each case. Charge-transfer complexes have been prepared, using TCNQ or TCNQF4 as the electron acceptor, with conductivities in the range of 104 to 0.22Scm1. Compounds 4 and 5 have been studied by X-ray crystallography; the former exhibits kappa-packing whilst the latter shows a high degree of conjugation between the two donor moieties.

References

1. Recent reviews: (a) M. R. Bryce, J. Mater. Chem., 1995, 5, 1481; (b) J. M. Williams, J. R. Ferraro, R. J. Thorn, K. D. Carlson, U. Geiser, H. H. Wang, A. M. Kini and M.-H. Whangbo, Organic Superconductors (Including Fullerenes); Synthesis, Structure, Properties and Theory, Prentice Hall, Englewood Cliffs, NJ, 1992; (c) G. Schukat and E. Fanghänel, Sulfur Rep., 1993, 14, 245.
2. (a) F. Wudl, G. M. Smith and E. J. Hufnagel, J. Chem. Soc., Chem. Commun., 1970, 1453; (b) S. Hünig, G. Kiesslich, D. Scheutzow, R. Zahradnik and P. Carsky, Int. J. Sulfur Chem. C, 1971, 6, 109; (c) G. Kiesslich, Ph.D. Thesis, University of Würzburg, 1968.
3. Recent synthetic reviews: (a) M. C. Grossel and S. C. Weston, Contemp. Org. Synth., 1994, 1, 367; (b) N. Svenstrup and J. Becher, Synthesis, 1995, 215.
4. A. J. Moore, P. J. Skabara, M. R. Bryce, A. S. Batsanov, J. A. K. Howard and S. T. A. K. Daley, J. Chem. Soc., Chem. Commun., 1993, 417; M. R. Bryce, P. J. Skabara, A. J. Moore, A. S. Batsanov, J. A. K. Howard and V. J. Hoy, Tetrahedron, 1997, 53, 17781.
5. K. Zong, W. Chen, M. P. Cava and R. D. Rogers, J. Org. Chem., 1996, 61, 8117.
6. (a) R. Ketcham, A.-B. Hörnfeldt and S. Gronowitz, J. Org. Chem., 1984, 49, 1117; (b) C. S. Wang, A. Ellern, J. Y. Becker and J. Bernstein, Adv. Mater., 1995, 7, 644.
7. (a) P. Shu, L. Chiang, T. Emge, D. Holt, T. Kistenmacher, M. Lee, J. Stokes, T. Poehler, A. Bloch and D. Cowan, J. Chem. Soc., Chem. Commun., 1981, 920; (b) M. Iyoda, Y. Kuwatani, N. Ueno and M. Oda, J. Chem. Soc., Chem. Commun., 1992, 158; (c) A. Charlton, A. E. Underhill, G. Williams, M. Kalaji, P. J. Murphy, K. M. Adbul Malik and M. B. Hursthouse, J. Org. Chem., 1997, 62, 3098; (d) M. R. Bryce, A. D. Chissel, J. Gopal, P. Kathirgamanathan and D. Parker, Synth. Met., 1991, 39, 397; (e) C. Thobie-Gautier, A. Gorgues, M. Jubault and J. Roncali, Macromolecules, 1993, 26, 4094; (f) for a general review see J. Roncali, J. Mater. Chem., 1997, 7, 2307; (g) T. Yamamoto and T. Shimizu, J. Mater. Chem., 1997, 7, 1967.
8. (a) M. J. Cook, G. Cooke and A. Jafari-Fini, Chem. Commun., 1996, 1925; (b) M. A. Blower, M. R. Bryce and W. Devonport, Adv. Mater., 1996, 8, 63.
9. (a) M. Prato, M. Maggini, C. Giacometti, G. Scorrano, G. Sandonà and G. Farina, Tetrahedron, 1996, 52, 5221; (b) N. Martín, L. Sánchez, C. Seoane, R. Andreu, J. Garín and J. Orduna, Tetrahedron Lett., 1996, 33, 5979; (c) J. Llacay, M. Mas, E. Molins, J. Veciana, D. Powell and C. Rovira, Chem. Commun., 1997, 659.
10. P. J. Skabara and K. Müllen, Synth. Met., 1997, 84, 345.
11. L. Chiang, P. Shu, D. Holt and D. Cowan, J. Org. Chem., 1983, 48, 4713.
12. M. A. Fox and H.-L. Pan, J. Org. Chem., 1994, 59, 6519.
13. C. Rovira, N. Santaló and J. Veciana, Tetrahedron Lett., 1989, 30, 7249; C. Rovira, J. Veciana, N. Santaló, J. Tarrés, J. Cirujeda, E. Molins, J. Llorca and E. Espinosa, J. Org. Chem., 1994, 59, 3307.
14. G. Saito, Pure Appl. Chem., 1987, 59, 999.
15. (a) C. S. Wang, A. Ellern, V. Khodorkovsky, J. Bernstein and J. Y. Becker, J. Chem. Soc., Chem. Commun., 1994, 983; (b) A. S. Batsanov, A. J. Moore, N. Robertson, A. Green, M. R. Bryce, J. A. K. Howard and A. E. Underhill, J. Mater. Chem., 1997, 7, 387.
16. (a) D. L. Lichtenberger, R. L. Johnston, K. Hinkelmann, T. Suzuki and F. Wudl, J. Am. Chem. Soc., 1990, 112, 3302; (b) A. J. Moore and M. R. Bryce, J. Chem. Soc., Chem. Commun., 1991, 1638.
17. R. J. Waltman, J. Bargon and A. F. Diaz, J. Phys. Chem., 1983, 87, 1459.
18. J. Roncali, Chem. Rev., 1992, 92, 711.
19. J. P. Ruiz, K. Nayak, D. S. Marynick and J. R. Reynolds, Macromolecules, 1989, 22, 1231.
20. S. Tanaka, M. Sato and K. Kaeriyama, Synth. Met., 1988, 25, 277.
21. R. J. Waltman and J. Bargon, Can. J. Chem., 1986, 64, 76.
22. F. Wudl, M. Kobayashi and A. J. Heeger, J. Org. Chem., 1984, 49, 3382.
23. F. Wudl and M. R. Bryce, J. Chem. Educ., 1990, 67, 717.
24. J. S. Chappel, A. N. Bloch, W. A. Bryden, M. Maxfield, T. O. Poehler and D. O. Cowan, J. Am. Chem. Soc., 1981, 103, 2442 Exceptions to the linear dependence of the nitrile stretching frequency with the degree of CT in TCNQ salts have been noted on several occasions: F. Bigoli, P. Deplano, F. A. Devillanova, A. Girlando, V. Lippolis, M.-L. Mercuri, M.-A. Pellinghelli and E. F. Trogu, J. Mater. Chem., 1998, 8, 1145 and references therein.
25. R. S. Rowland and R. Taylor, J. Phys. Chem., 1996, 100, 7384.
26. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, Suppl., 1.
27. G. M. Sheldrick, SHELXTL, Version 5, Siemens Analytical Instruments, Madison, WI, USA, 1995.
28. TEXSAN, TEXRAY Structural Analysis Package, Molecular Structure Corporation, The Woodlands, TX77381, USA.
29. S. Gronowitz and P. Moses, Acta Chem. Scand., 1962, 16, 105.