Probing magnetic exchange interactions in molecular magnets: an inclusion compound of a dithiadiazolyl radical

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

Philip. J. Langley, Jeremy M. Rawson, J. Nicholas B. Smith, Matthias Schuler, Rainer Bachmann, Arthur Schweiger, Fernando Palacio, Guillermo Antorrena, Georg Gescheidt, Andrea Quintel, Peter Rechsteiner and Jürg Hulliger


Abstract

Co-sublimation of the dithiadiazolyl radical, p-NCC6H4CNSSN 2 with the inclusion-forming host compound perhydrotriphenylene (PHTP) leads to trichroic crystals of the host-guest complex [PHTP-2]. Molecules of 2 are linked through a CN‥S interaction (ca. 3.03 Å) to form polar chains within the channels of the PHTP host lattice. The host-guest ratio is approximately 5:1. Pyroelectric and non-linear optic responses indicate that crystals of [PHTP-2] are macroscopically polar. A combination of variable temperature solid state EPR spectroscopy and magnetic susceptibility measurements are used to probe the electronic properties of [PHTP-2]; whilst [PHTP-2] is paramagnetic, no exchange coupling between neighbouring molecules of 2 within the channels could be established. The implications of these results on the magnetic exchange pathway of the weak ferromagnet, β-p-NCC6F4CNSSN β-1, are discussed.


References

  1. (a) J. S. Miller and A. J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385 CrossRef; (b) S. Nakatsuji and H. Anzai, J. Mater. Chem., 1997, 7, 2161 RSC.
  2. J. S. Miller, Adv. Mater., 1992, 4, 298 CrossRef CAS and references therein.
  3. A. J. Banister, N. Bricklebank, I. Lavender, J. M. Rawson, C. I. Gregory, B. K. Tanner, W. Clegg, M. R. J. Elsegood and F. Palacio, Angew. Chem., Int. Ed. Engl., 1996, 35, 2533 CrossRef CAS.
  4. F. Palacio, G. Antorrena, M. Castro, R. Burriel, J. Rawson, J. N. B. Smith, N. Bricklebank, J. Novoa and C. Ritter, Phys. Rev. Lett., 1997, 79, 2336 CrossRef CAS.
  5. R. L. Carlin, Magnetochemistry, Springer, Berlin, 1989 Search PubMed.
  6. R. Hoss, O. König, V. Kramer-Hoss, U. Berger, P. Rogin and J. Hulliger, Angew. Chem., Int. Ed. Engl., 1996, 35, 1664 CrossRef CAS.
  7. (a) J. Hulliger, P. Rogin, A. Quintel, P. Rechsteiner, O. König and M. Wübbenhorst, Adv. Mater., 1997, 9, 677 CAS; (b) J. Hulliger, P. J. Langley, O. König, S. W. Roth, A. Quintel and P. Rechsteiner, Pure Appl. Opt., 1998, 7, 221 CrossRef CAS.
  8. Several inclusion-forming compounds such as thiourea and PHTP have been used, for example, to stabilise radicals generated in situ, or to probe anisotropic molecular motion and dynamics of certain stable nitroxides (e.g., see O. Rohde and O. H. Griffit, J. Magn. Reson., 1975, 17, 324; B. J. Gaffne, J. Phys. Chem., 1979, 83, 3345). To the best of our knowledge, no other studies of magnetic exchange pathways between radicals located within the partially isolated confines of an inclusion lattice have been reported Search PubMed.
  9. A. W. Cordes, R. C. Haddon, R. G. Hicks, R. T. Oakley and T. T. M. Palstra, Inorg. Chem., 1992, 31, 1802 CrossRef CAS.
  10. J. M. Rawson, A. J. Banister and I. Lavender, Adv. Heterocycl. Chem., 1995, 62, 137.
  11. H. U. Hofs, J. W. Bats, R. Gleiter, G. Hartmann, R. Mews, M. Eckert-Maksic, H. Oberhammer and G. M. Sheldrick, Chem. Ber., 1985, 118, 3781 CrossRef.
  12. (a) O. König, H.-B. Bürgi, T. Armbruster, J. Hulliger and T. Weber, J. Am. Chem. Soc., 1997, 119, 10632 CrossRef; (b) J. Hulliger, O. König and R. Hoss, Adv. Mater., 1995, 7, 719 CAS.
  13. (a) J. Hulliger, A. Quintel, M. Wübbenhorst, P. J. Langley, S. W. Roth and P. Rechsteiner, Opt. Mater., 1998, 9, 259 CrossRef CAS; (b) A. Quintel, J. Hulliger and M. Wübbenhorst, J. Phys. Chem. B, 1998, 102, 4277 CrossRef CAS.
  14. (a) S. A. Fairhurst, K. M. Johnson, L. H. Sutcliffe, K. F. Preston, A. J. Banister, Z. V. Hauptman and J. Passmore, J. Chem. Soc., Dalton Trans., 1986, 1465 RSC; (b) S. A. Fairhurst, R. S. Pilkington and L. H. Sutcliffe, J. Chem. Soc., Faraday Trans. 1, 1983, 79, 439 RSC.
  15. Preliminary ab initio calculations (H.-P. Lüthi, J. Hulliger and J. M. Rawson, unpublished results) indicate, however, that there is an excited state in which a considerable percentage of the unpaired spin density is delocalized into the phenyl ring; this opens up the possibility of optically pumping the system to bring about intra-chain magnetic coupling in the inclusion lattice. Further studies are in progress.
  16. J. Hulliger, Angew. Chem., Int. Ed. Engl., 1994, 33, 143 CrossRef.
Click here to see how this site uses Cookies. View our privacy policy here.