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Ruthenium(II)-bis(4′-(4-ethynylphenyl)-2,2′:6′, 2″-terpyridine) — A versatile synthon in supramolecular chemistry. Synthesis and characterization

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Central European Journal of Chemistry

Abstract

A homoleptic ethynyl-substituted ruthenium(II)-bisterpyridine complex representing a versatile synthon in supramolecular chemistry was synthesized and analyzed by NMR spectroscopy, mass spectrometry and X-ray diffractometry. Furthermore, its photophysical properties were detailed by UV/Vis absorption, emission and resonance Raman spectroscopy. In order to place the results obtained in the context of the vast family of ruthenium coordination compounds, two structurally related complexes were investigated accordingly. These reference compounds bear either no or an increased chromophore in the 4′-position. The spectroscopic investigations reveal a systematic bathochromic shift of the absorption and emission maximum upon increasing chromophore size. This bathochromic shift of the steady state spectra occurs hand in hand with increasing resonance Raman intensities upon excitation of the metal-to-ligand charge-transfer transition. The latter feature is accompanied by an increased excitation delocalization over the chromophore in the 4′-position of the terpyridine. Thus, the results presented allow for a detailed investigation of the electronic effects of the ethynyl substituent on the metal-to-ligand charge-transfer states in the synthon for click reactions leading to coordination polymers.

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References

  1. A. Wild, A. Winter, F. Schlütter, U.S. Schubert, Chem. Soc. Rev. 40, 1459 (2011)

    Article  CAS  Google Scholar 

  2. W.K. Chan, X. Gong, W.Y. Ng, Appl. Phys. Lett. 71, 2919 (1997)

    Article  CAS  Google Scholar 

  3. W.Y. Ng, W.K. Chan, Adv. Mater. 9, 716 (1991)

    Article  Google Scholar 

  4. W.Y. Ng, X. Gong, W.K. Chan, Chem. Mater. 11, 1165 (1999)

    Article  CAS  Google Scholar 

  5. P.D. Vellis, J.A. Mikroyannidis, C.N. Lo, C.S. Hsu, J. Polym. Sci., Part A: Polym. Chem. 46, 7702 (2008)

    Article  CAS  Google Scholar 

  6. A. Wild, F. Schlütter, G.M. Pavlov, C. Friebe, G. Festag, A. Winter, M.D. Hager, V. Cimrova, U.S. Schubert, Macromol. Rapid Commun. 31, 868 (2010)

    Article  CAS  Google Scholar 

  7. U.S. Schubert, C. Eschbaumer, G. Hochwimmer, Synthesis 779 (1999)

  8. V. Grosshenny, A. Harriman, R. Ziessel, Angew. Chem. Int. Ed. 34, 2705 (1995)

    CAS  Google Scholar 

  9. B.G.G. Lohmeijer, U.S. Schubert, Macromol. Chem. Phys. 204, 1072 (2003)

    Article  CAS  Google Scholar 

  10. A.C. Benniston, A. Harriman, P. Li, C.A. Sams, J. Am. Chem. Soc. 127, 2553 (2005)

    Article  CAS  Google Scholar 

  11. U.S. Schubert, H. Hofmeier, G.R. Newkome, Modern Terpyridine Chemistry (Wiley-VHC, Weinheim, 2006)

    Book  Google Scholar 

  12. J. Hjelm, E.C. Constable, E. Figgemeier, A. Hagfeldt, R. Handel, C.E. Housecroft, E. Mukhtarb, E. Schofield, Chem. Commun. 284 (2002)

  13. S. Kelch, M. Rehahn, Macromolecules 32, 5818 (1999)

    Article  CAS  Google Scholar 

  14. O. Schmelz, M. Rehahn, e-Polymers 47, 1 (2002)

    Google Scholar 

  15. A. Winter, A. Wild, R. Hoogenboom, M.W.M. Fijten, M.D. Hager, R.A. Fallahapour, U.S. Schubert, Synthesis 1506 (2009)

  16. D. Fournier, R. Hoogenboom, U.S. Schubert, Chem. Soc. Rev. 36, 1369 (2007)

    Article  CAS  Google Scholar 

  17. U. Mansfeld, C. Pietsch, R. Hoogenboom, C.R. Becer, U.S. Schubert, Polym. Chem. 1, 1560 (2010)

    Article  CAS  Google Scholar 

  18. H. Hofmeier, S. Schmatloch, D. Wouters, U.S. Schubert, Macromol. Chem. Phys. 204, 2197 (2003)

    Article  CAS  Google Scholar 

  19. V. Marin, E. Holder, R. Hoogenboom, U.S. Schubert, Chem. Soc. Rev. 36, 618 (2007)

    Article  CAS  Google Scholar 

  20. R. Ziessel, V. Grosshenny, M. Hissler, C. Stroh, Inorg. Chem. 43, 4262 (2004)

    Article  CAS  Google Scholar 

  21. E. Alessio, Chem. Rev. 104, 4203 (2004)

    Article  CAS  Google Scholar 

  22. A. Winter, D. A.M. Egbe, U.S. Schubert, Org. Lett. 9, 2345 (2007)

    Article  CAS  Google Scholar 

  23. D. Chartrand, I. Theobald, G.S. Hanan, Acta Crystallogr., Sect. E: Struct. Rep. Online 63, 1561 (2007)

    Article  Google Scholar 

  24. A.C. Benniston, G. Chapman, A. Harriman, M. Mehrabi, C.A. Sams, Inorg. Chem. 43, 4227 (2004)

    Article  CAS  Google Scholar 

  25. A. Harriman, A. Khatyr, R. Ziessel, A.C. Benniston, Angew. Chem. Int. Ed. 39, 4287 (2000)

    Article  CAS  Google Scholar 

  26. S. Welter, N. Salluce, A. Benetti, N. Rot, P. Belser, P. Sonar, A.C. Grimsdale, K. Müllen, M. Lutz, A.L. Spek, L. De Cola, Inorg. Chem. 44, 4706 (2005)

    Article  CAS  Google Scholar 

  27. J.S. Bair, R.G. Harrison, J. Org. Chem. 72, 6653 (2007)

    Article  CAS  Google Scholar 

  28. M. Hissler, A. El-ghayoury, A. Harriman, R. Ziessel, Angew. Chem. Int. Ed. 37, 1717 (1998)

    Article  CAS  Google Scholar 

  29. M. Presselt, B. Dietzek, M. Schmitt, J. Popp, A. Winter, M. Chiper, C. Friebe, U.S. Schubert, J. Phys. Chem. C 112, 18651 (2008)

    CAS  Google Scholar 

  30. M. Preselt, B. Dietzek, M. Schmitt, S. Rau, A. Winter, M. Jäger, U.S. Schubert, J. Popp, J. Phys. Chem. A 114, 13163 (2010)

    Article  Google Scholar 

  31. A. Cannizzo, F. van Mourik, W. Gawelda, G. Zgrablic, C. Bressler, M. Chergui, Angew. Chem. Int. Ed. 45, 3174 (2006)

    Article  CAS  Google Scholar 

  32. R. Siebert, D. Akimov, M. Schmitt, A. Winter, U.S. Schubert, B. Dietzek, J. Popp, ChemPhysChem 10, 910 (2009)

    Article  CAS  Google Scholar 

  33. R. Siebert, A. Winter, U.S. Schubert, B. Dietzek, J. Popp, J. Phys. Chem. C 114, 6841 (2010)

    Article  CAS  Google Scholar 

  34. R. Siebert, A. Winter, U.S. Schubert, B. Dietzek, J. Popp, Phys. Chem. Chem. Phys. 13, 1606 (2011)

    CAS  Google Scholar 

  35. R. Siebert, C. Hunger, J. Guthmuller, F. Schlütter, A. Winter, U.S. Schubert, L. González, B. Dietzek, J. Popp, J. Phys. Chem. C, 115, 12677 (2011)

    Article  CAS  Google Scholar 

  36. A. Amini, A. Harriman, A. Mayeux, Phys. Chem. Chem. Phys. 6, 1157 (2004)

    Article  CAS  Google Scholar 

  37. B. J. Coe, D.W. Thompson, C.T. Cilbertson, J.R. Schoonover, T.J. Meyer, Inorg. Chem. 34, 3385 (1995)

    Article  CAS  Google Scholar 

  38. R. Siebert, A. Winter, B. Dietzek, U.S. Schubert, J. Popp, Macromol. Rapid Commun. 31, 883 (2010)

    Article  CAS  Google Scholar 

  39. E.C. Glazer, D. Magde, Y. Tor, J. Am. Chem. Soc. 127, 4190 (2005)

    Article  CAS  Google Scholar 

  40. E.C. Glazer, D. Magde, Y. Tor, J. Am. Chem. Soc. 129, 8544 (2007)

    Article  CAS  Google Scholar 

  41. H. Yersin, E. Gallhuber, A. Vogler, H. Kunkelyt, J. Am. Chem. Soc. 105, 4155 (1983)

    Article  CAS  Google Scholar 

  42. A.B. Myers, Chem. Rev. 96, 911 (1996)

    Article  CAS  Google Scholar 

  43. M. Schwalbe, M. Karnahl, H. Görls, D. Chartrand, F. Laverdiere, G.S. Hanan, S. Tschierlei, B. Dietzek, M. Schmitt, J. Popp, J. G. Vos, S. Rau, Dalton Trans. 4012 (2009)

  44. S. Tschierlei, B. Dietzek, M. Karnahl, S. Rau, F.M. MacDonnell, M. Schmitt, J. Popp, J. Raman Spectrosc. 39, 557 (2008)

    Article  CAS  Google Scholar 

  45. P.W. Hansen, P.W. Jensen, Spectrochim. Acta. 50A, 169 (1993)

    Google Scholar 

  46. R.J.H. Clark, P.C. Turtle, D.P. Strommen, B. Streusand, J. Kincaid, K. Nakamoto, Inorg. Chem. 16, 84 (1977)

    Article  CAS  Google Scholar 

  47. A. Winter, C. Friebe, M. Chiper, U.S. Schubert, M. Presselt, B. Dietzek, M. Schmitt, J. Popp, ChemPhysChem 10, 787 (2009)

    Article  CAS  Google Scholar 

  48. S. Tschierlei, M. Karnahl, M. Presselt, B. Dietzek, J. Guthmuller, L. González, M. Schmitt, S. Rau, J. Popp, Angew. Chem. Int. Ed. 49, 3981 (2010)

    CAS  Google Scholar 

  49. U.S. Schubert, C. Eschbaumer, P.R. Andres, H. Hofmeier, C.H. Weidl, E. Herdtweck, E. Dulkeith, A. Morteani, N.E. Hecker, J. Feldmann, Synth. Metals 121, 1249 (2001)

    Article  CAS  Google Scholar 

  50. A. Winter, C. Friebe, M.D. Hager, U.S. Schubert, Eur. J. Org. Chem. 801 (2009)

  51. R. Hooft, COLLECT Data Collection Software (Nonius B.V., Delft, The Netheralnds, 1998)

    Google Scholar 

  52. Z. Otwinowski, W. Minor, In: C.W. Carter, R.M. Sweet (Eds.), Processing of X-Ray Diffraction Data Collected in Oscillation Mode in Methods in Enzymology in Macromolecular Crystallography (Academic Press, San Diego, USA, 1997) Part A, Vol. 276, p.307

    Google Scholar 

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Author information

Authors and Affiliations

  1. Institute for Physical Chemistry, Jena Center for Soft Matter (JCSM), and Abbe Center of Photonics (ACP) Friedrich-Schiller-University Jena, 07743, Jena, Germany

    Ronald Siebert, Benjamin Dietzek & Jürgen Popp

  2. Laboratory of Organic and Macromolecular Chemistry (IOMC) and Jena Center for Soft Matter (JCSM) Friedrich-Schiller-University Jena, 07743, Jena, Germany

    Florian Schlütter, Andreas Winter & Ulrich S. Schubert

  3. Institute for Physics, Ilmenau University of Technology, 98693, Ilmenau, Germany

    Martin Presselt

  4. Laboratory of Inorganic and Analytical Chemistry, Friedrich-Schiller-University Jena, 07743, Jena, Germany

    Helmar Görls

  5. Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX, Eindhoven, The Netherlands

    Ulrich S. Schubert

  6. Institute of Photonic Technology (IPHT) Jena, 07745, Jena, Germany

    Benjamin Dietzek & Jürgen Popp

Authors
  1. Ronald Siebert
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  2. Florian Schlütter
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  3. Andreas Winter
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  4. Martin Presselt
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  6. Ulrich S. Schubert
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  8. Jürgen Popp
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Correspondence to Ulrich S. Schubert.

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Siebert, R., Schlütter, F., Winter, A. et al. Ruthenium(II)-bis(4′-(4-ethynylphenyl)-2,2′:6′, 2″-terpyridine) — A versatile synthon in supramolecular chemistry. Synthesis and characterization. cent.eur.j.chem. 9, 990–999 (2011). https://doi.org/10.2478/s11532-011-0087-6

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  • DOI: https://doi.org/10.2478/s11532-011-0087-6

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