Perylene derivative charge transfer salts: synthesis, crystal structure and characterisation of (pet)₃[Ni(mnt)₂]₂

Abstract

(pet)₃ [Ni(mnt)₂ ]₂ single crystals, where pet=perilo[1,12-b,c,d]thiophene and mnt= maleonitriledithiolate (cis-2,3-dimercapto-butene-2,3-dinitrile), were obtained by electrocrystallisation from dichloromethane solutions of pet and the tetrabutylammonium salt of [Ni(mnt)₂ ]^– . The crystal structure is triclinic, space group P1, with cell parameters a=10.2972(9), b=11.5037(12), c=13.3297(10) Å, alpha;=78.320(8) °, beta;=87.096(7) °, gamma;=87.785(8) °, Z=1 and consists of segregated stacks along a of partially oxidised pet molecules arranged as trimers, (pet)₃²⁺ , and dimerised [Ni(mnt)₂ ]^– anions. The electrical properties are typical of a semiconductor with room-temperature conductivity of ca. 9 S cm^–1 with an activation energy of 168 meV, and the paramagnetic susceptibility is due to a singlet–triplet type contribution of antiferromagnetically coupled pairs of S=1/2 spins of the [Ni(mnt)₂ ]^– species with J/k_B=–226 K.

References

1. For a review, see: M. Almeida and R. T. Henriques, in Handbook of Organic Conductive Molecules and Polymers, ed. H. S. Nalwa, John Wiley and Sons, Chichester, 1997, vol. 1, ch. 2, p. 87.
2. B. Hilti, C. W. Mayer and G. Rihs, Solid State Commun., 1981, 38, 1129.
3. J. Morgado, I. C. Santos, R. T. Henriques, M. Fourmigué, P. Matias, L. F. Veiros, M. J. Calhorda, M. T. Duarte, L. Alcácer and M. Almeida, Chem. Mater., 1994, 6, 2309.
4. R. Lapouyade, J. P. Morand, D. Chasseau, C. Haw and P. Delhaès, J. Phys. (Paris) Coll., 1983, 44, C3-1235.
5. P. Penven, D. Jérôme, S. Ravy, P. A. Albouy and P. Batail, Synth. Met., 1988, 27, B405; V. Ilakovac, S. Ravy, A. Moradpour, L. Firlej and P. Bernier, Phys. Rev. B, 1995, 52, 4108; P. Michel, A. Moradpour, P. Penven, L. Firlej, P. Bernier, B. Levy, S. Ravy and A. Zahab, J. Am. Chem. Soc., 1990, 112, 8285.
6. V. I. Rogovik, J. Org. Chem. (USSR), 1974, 10, 1072.
7. L. Alcácer, J. Morgado, R. T. Henriques and M. Almeida, Synth. Met., 1995, 70, 1093.
8. S. Iwashima and J. Aoki, Bull. Chem. Soc. Jpn., 1968, 41, 2789.
9. A. Davison and R. H. Holm, Inorg. Synth., 1967, 10, 8.
10. G. M. Sheldrick, SHELXS-86: Program for the Solution of Crystal Structure, University of Göttingen, 1986.
11. G. M. Sheldrick, SHELXL-93: Program for Crystal Structure Refinement, University of Göttingen, 1993.
12. P. M. Chaikin and J. F. Kwak, Rev. Sci. Instrum., 1975, 46, 218.
13. R. P. Huebner, Phys. Rev., 1964, 135, A1281.
14. P. E. Schaffer, F. Wudl, G. A. Thomas, J. P. Ferraris and D. O. Cowan, Solid State Commun., 1974, 14, 347.
15. V. Gama, M. Almeida, R. T. Henriques, I. C. Santos, A. Domingos, S. Ravy and J. P. Pouget, J. Phys. Chem., 1991, 95, 4263.
16. V. Gama, R. T. Henriques, G. Bonfait, L. C. Pereira, J. C. Waerenborgh, I. C. Santos, M. T. Duarte, J. M. P. Cabral and M. Almeida, Inorg. Chem., 1992, 31, 2598.
17. L. Alcácer, H. Novais, F. Pedroso, S. Flandrois, C. Coulon, D. Chasseau and J. Gaultier, Solid State Commun., 1980, 35, 945.
18. A. Domingos, R. T. Henriques, V. Gama, M. Almeida, A. Lopes Vieira and L. Alcácer, Synth. Met., 1989, 27, B411.
19. V. Gama, R. T. Henriques, M. Almeida, L. Veiros, M. J. Calhorda, A. Meetsma and J. L. de Boer, Inorg. Chem., 1993, 32, 3705.
20. I. C. Santos, J. Morgado, T. L. Duarte, L. Alcácer and M. Almeida, Acta Crystallogr., Sect. C, in press.
21. C. J. Fritsch Jr., Acta Crystallogr., 1966, 20, 107.
22. A. Kobayashi and Y. Sasaki, Bull. Chem. Soc. Jpn., 1977, 50, 2650.
23. C. Mahadevan, M. Seshasayee, B. V. R. Murthy, P. Kuppusamy and P. T. Manoharan, Acta Crystallogr., Sect. C, 1983, 39, 1335.
24. R. Hoffmann and W. N. Lipscomb, J. Chem. Phys., 1962, 36, 2179; 1962, 37, 2872; R. Hoffmann, J. Chem. Phys., 1963, 39, 1397.
25. J. H. Ammeter, H. B. Bürgi, J. C. Thibeault and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 3686.
26. L. F. Veiros, M. J. Calhorda and E. Canadell, Inorg. Chem., 1994, 33, 4290.
27. M. H. Whangbo, J. M. Williams, P. C. W. Leung, M. A. Beno, T. J. Emge and H. H. Wang, Inorg. Chem., 1985, 24, 3500; M. H. Whangbo, J. M. Williams, P. C. W. Leung, M. A. Beno, T. J. Emge, H. H. Wang, K. D. Carlson and G. W. Crabtree, J. Am. Chem. Soc., 1985, 107, 5815.
28. J. A. Ayllón, I. C. Santos, R. T. Henriques, M. Almeida, E. B. Lopes, J. Morgado, L. Alcácer, L. F. Veiros and M. T. Duarte, J. Chem. Soc., Dalton Trans., 1995, 3543.
29. M. H. Whangbo and R. Hoffmann, J. Am. Chem. Soc., 1978, 100, 6093; M. H. Whangbo, W. M. Walsh, jun., R. C. Haddon and F. Wudl, Solid State Commun., 1982, 43, 637; M. H. Whangbo, J. M. Williams, M. A. Beno and J. R. Dorfman, J. Am. Chem. Soc., 1983, 105, 645.
30. B. Bleaney and K. D. Bowers, Proc. R. Soc. London Ser. A, 1952, 214, 351.
31. J. F. Weiher, L. R. Melby and R. E. Benson, J. Am. Chem. Soc., 1964, 86, 4329.
32. A. E. Underhill, P. I. Clemenson, M. B. Hursthouse, R. L. Short, G. J. Ashwell, I. M. Sandy and K. Carneiro, Synth. Met., 1987, 19, 953.
33. A. T. Coomber, D. Beljonne, R. H. Friend, J. L. Brédas, A. Charlton, N. Robertson, A. E. Underhill, M. Kurmoo and P. Day, Nature (London), 1996, 380, 144.
34. M. C. Cross and D. S. Fischer, Phys. Rev. B, 1979, 19, 402.
35. J. V. Rodrigues, I. C. Santos, V. Gama, R. T. Henriques, J. C. Waerenborgh, M. T. Duarte and M. Almeida, J. Chem. Soc., Dalton Trans., 1994, 2655.