Unexpected Formation of a Doubly Bridged Cyclo-1,2-dithian 1D Coordination Cu2I2-Containing Luminescent Polymer

  • Michael Knorr
  • Fabrice Guyon
  • Abderrahim Khatyr
  • Magali Allain
  • Shawkat M. Aly
  • Antony Lapprand
  • Daniel Fortin
  • Pierre D. Harvey


CuI reacts instantaneously with butanedithiol in MeCN solution to form a sparingly soluble and thermally stable colorless polymeric material 1 of composition [(Cu2I2){HS(CH2)4SH}] n . Raman and IR spectroscopy confirm the presence of Cu(I) bound S–H functions. Furthermore, small amounts of the yellow compound [{Cu(μ2-I)2Cu}(C4H8S2)2] n 2 co-crystallize after several days. If the reaction mixture is exposed to air, polymeric 2 is isolated as the main product. An X-ray diffraction study reveals that 1D polymer 2 is assembled by rhomboid Cu(μ2-I)2Cu clusters (d Cu···Cu 2.6843(18) Å), which are linked through the S-atoms of six-membered 1,2-dithian heterocycles, thus generating an infinite ribbon. The low-frequency region in the Raman spectra show a striking similarity suggesting that polymers 1 and 2 bear the same cluster rhomboid Cu(μ2-I)2Cu clusters. The photophysics and luminescence properties of 2 have been studied experimentally and by means of DFT/TDDFT calculations.

Graphical Abstract

CuI reacts with HS(CH2)4SH to form a polymer of composition [(Cu2I2){HS(CH2)4SH}]n which slowly oxidizes to the luminescent [{Cu(μ2-I)2Cu}(C4H8S2)2]n polymer. The latter exhibits a 1D chain assembled by rhomboid Cu(μ2-I)2Cu clusters linked through the S-atoms of six-membered 1,2-dithian heterocycles. The luminescence properties of this polymer have been studied experimentally and by means of DFT/TDDFT calculations.


Coordination polymer Copper Thiol Dithian DFT/TDDFT computations Thermogravimetric analysis Raman 



PDH thanks NSERC (Natural Sciences and Engineering Research Council of Canada), FQRNT (Fonds Québécois pour la Recherche en Sciences de la Nature et la Technologie) and CEMOPUS (Centre sur les Matériaux Optiques et Photoniques de l’Université de Sherbrooke) for fundings. Financial support from the council of the Région of Franche-Comté for the acquisition of a fluorescence spectrometer is also gratefully acknowledged.

Supplementary material

10904_2010_9389_MOESM1_ESM.doc (4.1 mb)
Supplementary material 1 (DOC 4231 kb)


  1. 1.
    J.-R. Li, X.-H. Bu, Eur. J. Inorg. Chem. 27 (2008)Google Scholar
  2. 2.
    M. Knorr, F. Guyon, Luminescent oligomeric and polymeric copper coordination compounds assembled by thioether ligands, in Macromolecules Containing Metal and Metal-Like Elements: Photophysics and Photochemistry of Metal-Containing Polymers, vol. 10, ed. by A.S. Abd-El Aziz, C.E. Carraher, C.U. Pittman, M. Zeldin (Wiley, New York, 2010), pp. 89–158Google Scholar
  3. 3.
    J.R. Black, W. Levason, J. Chem. Soc. Dalton Trans. 3225 (1994)Google Scholar
  4. 4.
    J.R. Black, N.R. Champness, W. Levason, G. Reid, J. Chem. Soc. Dalton Trans. 3439 (1995)Google Scholar
  5. 5.
    M.O. Awaleh, A. Badia, F. Brisse, Inorg. Chem. 44, 7833 (2005)CrossRefGoogle Scholar
  6. 6.
    X.-H. Bu, W. Chen, W.-F. Hou, M. Du, R.-H. Zhang, F. Brisse, Inorg. Chem. 41, 3477 (2002)CrossRefGoogle Scholar
  7. 7.
    M.O. Awaleh, A. Badia, F. Brisse, X.-H. Bu, Inorg. Chem. 45, 1560 (2006)CrossRefGoogle Scholar
  8. 8.
    M.O. Awaleh, F. Baril-Robert, C. Reber, A. Badia, F. Brisse, Inorg. Chem. 47, 2964 (2008)CrossRefGoogle Scholar
  9. 9.
    M. Knorr, F. Guyon, A. Khatyr, C. Däschlein, C. Strohmann, S.M. Aly, A.S. Abd-El-Aziz, D. Fortin, P.D. Harvey, Dalton Trans. 948 (2009)Google Scholar
  10. 10.
    H.N. Peindy, F. Guyon, A. Khatyr, M. Knorr, C. Strohmann, Eur. J. Inorg. Chem. 1823 (2007)Google Scholar
  11. 11.
    C. Xie, L. Zhou, W. Feng, J. Wang, W. Chen, J. Mol. Struct. 921, 132 (2009)CrossRefGoogle Scholar
  12. 12.
    P.D. Harvey, M. Knorr, Macromol. Rapid Commun. 31, 808 (2010)CrossRefGoogle Scholar
  13. 13.
    A. Ulman, J. Am. Chem. Soc. 23, 1533 (1996)Google Scholar
  14. 14.
    K. Bandyopadhyay, K. Vijayamohanan, Langmuir 14, 6924 (1998)CrossRefGoogle Scholar
  15. 15.
    M. Brust, P.M. Blass, A.J. Bard, Langmuir 13, 5602 (1997)CrossRefGoogle Scholar
  16. 16.
    M. Heller, W.S. Sheldrick, Z. Anorg. Allg. Chem. 630, 1869 (2004)CrossRefGoogle Scholar
  17. 17.
    P.M. Boorman, K.A. Kerr, R.A. Kydd, K.J. Moynihan, K.A. Valentine, J. Chem. Soc. Dalton Trans. 1401 (1982)Google Scholar
  18. 18.
    R.D. Adams, M. Huang, S. Johnson, Concerning the reaction of CuI with 1,2,5,6-tetrathiacyclooctane and 1,2,5,6,9,10-hexathiacyclododecane. Polyhedron 17, 2755 (1998)Google Scholar
  19. 19.
    G.A. Bowmaker, J.V. Hanna, C. Pakawatchai, B.W. Skelton, Y. Thanyasirikul, A.H. White, Inorg. Chem. 48, 350 (2009)CrossRefGoogle Scholar
  20. 20.
    M.E. Helton, P. Chen, P.P. Paul, Z. Tyeklar, R.D. Sommer, L.N. Zakharov, A.L. Rheingold, E.I. Solomon, K.D. Karlin, J. Am. Chem. Soc. 125, 1160 (2003)CrossRefGoogle Scholar
  21. 21.
    H. Braunwarth, P. Lau, G. Huttner, M. Minelli, D. Guenauer, L. Zsolnai, I. Jibril, K. Evertz, J. Organomet. Chem. 411, 383 (1991)CrossRefGoogle Scholar
  22. 22.
    W. Lu, Z.-M. Yan, J. Dai, Y. Zhang, Q.-Y. Zhu, D.-X. Jia, W.-J. Guo, Eur. J. Inorg. Chem. 2339 (2005)Google Scholar
  23. 23.
    H. Maelger, F. Olbrich, J. Kopf, D. Abeln, E. Weiss, Z. Nat. B 47, 1276 (1992)Google Scholar
  24. 24.
    N.R. Brooks, A.J. Blake, N.R. Champness, P.A. Cooke, P. Hubberstey, D.M. Proserpio, C. Wilson, M. Schröder, J. Chem. Soc. Dalton Trans. 456 (2001)Google Scholar
  25. 25.
    H.W. Yim, D. Rabinovich, K.C. Lam, J.A. Golen, A.L. Rheingold, Acta Cryst. E E59, m556 (2003)CrossRefGoogle Scholar
  26. 26.
    M. Munakata, L.P. Wu, T. Kuroda-Sowa, M. Maekawa, Y. Suenaga, S. Nakagawa, J. Chem. Soc. Dalton Trans. 1525 (1996)Google Scholar
  27. 27.
    P.C. Ford, Coord. Chem. Rev. 132, 129 (1994)CrossRefGoogle Scholar
  28. 28.
    P.C. Ford, E. Cariati, J. Bourassa, Chem. Rev. 99, 3625 (1999)CrossRefGoogle Scholar
  29. 29.
    F.D. Angelis, S. Fantacci, A. Sgamellotti, E. Cariati, R. Ugo, P.C. Ford, Inorg. Chem. 45, 10576 (2006)CrossRefGoogle Scholar
  30. 30.
    M. Knorr, A. Pam, A. Khatyr, C. Strohmann, M.M. Kubicki, Y. Rousselin, S.M. Aly, D. Fortin, P.D. Harvey, Inorg. Chem. 49(13), 5834 (2010)CrossRefGoogle Scholar
  31. 31.
    N. Armaroli, G. Accorsi, F. Cardinali, A. Listorti, Top. Curr. Chem. 280, 69 (2007)CrossRefGoogle Scholar
  32. 32.
    K.R. Kyle, J. DiBenedetto, P.C. Ford, J. Chem. Soc. Chem. Commun. 714 (1989)Google Scholar
  33. 33.
    T.H. Kim, K.Y. Lee, Y.W. Shin, S.-T. Moon, K.-M. Park, J.S. Kim, Y. Kang, S.S. Leea, J. Kim, Inorg. Chem. Commun. 8, 27 (2005)CrossRefGoogle Scholar
  34. 34.
    T.H. Kim, Y.W. Shin, J.H. Jung, J.S. Kim, J. Kim, Angew. Chem. Int. Ed. Engl. 47, 685 (2008)CrossRefGoogle Scholar
  35. 35.
    M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Jr. Montgomery, R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, A.G. Baboul, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M. W. Gill, B.G. Johnson, W. Chen, M.W. Wong, J.L. Andres, M. Head-Gordon, E.S. Replogle and J.A. Pople, Gaussian 03 (Revision A.2) (Gaussian Inc., Pittsburgh, 1998)Google Scholar
  36. 36.
    P. Hohenberg, W. Kohn, Phys. Rev. 136, B864 (1964)CrossRefGoogle Scholar
  37. 37.
    W. Kohn, L.J. Sham, Phys. Rev. 140, B864 (1965)CrossRefGoogle Scholar
  38. 38.
    R.G. Parr, W. Yang, Functional Theory of Atoms and Molecules (Oxford University Press, Oxford, 1989)Google Scholar
  39. 39.
    D.R. Salahub, M.C. Zerner (ed.), The Challenge of d and f Electrons: Theory and Computation. ACS Symposium Series, vol. 394 (1989)Google Scholar
  40. 40.
    R.E. Stratmann, G.E. Scuseria, M.J. Frisch, J. Chem. Phys. 109, 8218 (1998)CrossRefGoogle Scholar
  41. 41.
    R. Bauernschmitt, R. Ahlrichs, Chem. Phys. Lett. 256, 454 (1996)CrossRefGoogle Scholar
  42. 42.
    M.E. Casida, C. Jamorski, K.C. Casida, D.R. Salahub, J. Chem. Phys. 108, 4439 (1998)CrossRefGoogle Scholar
  43. 43.
    A.D. Becke, J. Chem. Phys. 98, 5648 (1993)CrossRefGoogle Scholar
  44. 44.
    C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785 (1988)CrossRefGoogle Scholar
  45. 45.
    B. Miehlich, A. Savin, H. Stoll, H.-W. Preuss, Chem. Phys. Lett. 157, 200 (1989)CrossRefGoogle Scholar
  46. 46.
    J.S. Binkley, J.A. Pople, W.J. Hehre, J. Am. Chem. Soc. 102, 939 (1980)CrossRefGoogle Scholar
  47. 47.
    M.S. Gordon, J.S. Binkley, J.A. Pople, W.J. Pietro, W.J. Hehre, J. Am. Chem. Soc. 104, 2797 (1982)CrossRefGoogle Scholar
  48. 48.
    W.J. Pietro, M.M. Francl, W.J. Hehre, D.J. DeFrees, J.A. Pople, J.S. Binkley, J. Am. Chem. Soc. 104, 5039 (1982)CrossRefGoogle Scholar
  49. 49.
    K.D. Dobbs, W.J. Hehre, J. Comput. Chem. 7, 359 (1986)CrossRefGoogle Scholar
  50. 50.
    K.D. Dobbs, W.J. Hehre, J. Comput. Chem. 8, 861 (1987)CrossRefGoogle Scholar
  51. 51.
    K.D. Dobbs, W.J. Hehre, J. Comput. Chem. 8, 880 (1987)CrossRefGoogle Scholar
  52. 52.
    SBKJC ECP/VDZ Basis Set Exchange Library
  53. 53.
    W.J. Stevens, H. Basch, M. Krauss, M. J. Chem. Phys. 81, 6026 (1984)CrossRefGoogle Scholar
  54. 54.
    W.J. Stevens, M. Krauss, H. Basch, P.G. Jasien, Can. J. Chem. 70, 612 (1992)CrossRefGoogle Scholar
  55. 55.
    T.R. Cundari, W.J. Stevens, J. Chem. Phys. 98, 5555 (1993)CrossRefGoogle Scholar
  56. 56.
    N.M. O’boyle, A.L. Tenderholt, K.M. Langner, J. Comput. Chem. 29, 839 (2008)CrossRefGoogle Scholar
  57. 57.
    A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl. Crystallogr. 32, 115 (1993)CrossRefGoogle Scholar
  58. 58.
    SHELXL-97, Program for the Refinement of Crystal Structures, G.M. Sheldrick, University of Göttingen, Germany (1997)Google Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Michael Knorr
    • 1
  • Fabrice Guyon
    • 1
  • Abderrahim Khatyr
    • 1
  • Magali Allain
    • 2
  • Shawkat M. Aly
    • 3
  • Antony Lapprand
    • 3
  • Daniel Fortin
    • 3
  • Pierre D. Harvey
    • 3
  1. 1.Faculté des Sciences et des Techniques, Institut UTINAM UMR CNRS 6213Université de Franche-ComtéBesançonFrance
  2. 2.Laboratoire MOLTECH ANJOU UMR CNRS 6200Université d’AngersAngersFrance
  3. 3.Département de ChimieUniversité de SherbrookeSherbrookeCanada

Personalised recommendations