The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

  • Sébastien Clément
  • Shawkat Mohammed Aly
  • Karl Gagnon
  • Alaa S. Abd-El-Aziz
  • Michael Knorr
  • Pierre D. HarveyEmail author


ClPd(μ-dppm)2PtCl (1) reacts with (CNC6H4–2-OCH2–)2 to form a sparingly soluble and thermally stable orange polymeric material 4. 1 reacts with 1 or 2 equivalents of CNC6H4–2-OCH3 to form the soluble A-frame d8–d8 model complexes 2 [ClPd(μ-dppm)2(μ-CNR)PtCl], and 3 [ClPd(μ-dppm)2(μ-CNR)Pt(CNR)](Cl) (R = C6H4–2-OCH3), respectively. IR (ν(NC) bridging versus terminal) and NMR data reveal an A-frame structure where the terminal CNR ligands are bonded to Pt. 4 which is amorphous (XRD) appears stable up to 290 °C (TGA), but exhibits an exothermic process between 215 and 255 °C upon the first scan in DSC, but disappears upon the second. Two compounds, model 2e = 674 nm; τe = 0.38 ± 0.01 μs; Φe = 0.0079 (±10%)) and polymer 4 e = 660 nm; τe = 0.18 ± 0.01 μs; Φe = 0.0056 (±10%)) are luminescent at 77 K in the solid state and in fluid solution (PrCN).

Graphical abstract

The First A-Frame-Containing Organometallic Polymer: Taking Advantage of the Site Selectivity in PdPt-Mixed Metal Bimetallics

Sébastien Clément, Shawkat Mohammed Aly, Karl Gagnon, Alaa S. Abd-El-Aziz, Michael Knorr, Pierre D. Harvey

ClPd(μ-dppm)2Cl2 reacts with (CN–C6H4–O–CH2–)2 to form the first A-frame-containing organometallic polymer, which is unambiguously characterized with the use of model compounds. This polymer does not experience any weight loss up to 290 °C based on TGA measurements, but DSC traces reveal an irreversible process at 215 °C (DSC). The novel material is also luminescent at 77 K. For example, λe = 660 nm; τe = 0.18 ± 0.01 μs; Φe = 0.0056 (±10%) in PrCN.


A-frame Isocyanide Palladium Platinum Differential scanning calorimetry (DSC) Heterobimetallic Organometallic polymers Oligomers Thermogravimetric analysis (TGA) 



PDH thanks the Natural Science and Engineering Research Council of Canada (NSERC). MK thanks the French Ministère de la Recherche et Technologie for financial support and a PhD grant for SC.

Supplementary material

10904_2007_9176_MOESM1_ESM.doc (135 kb)
(DOC 135 kb)


  1. 1.
    (a) L. Han, M. Hong, Inorg. Chem. Commun. 8, 406 (2005); (b) Q. Ye, X.-S. Wang, H. Zhao, R.-G. Xiong, Chem. Soc. Rev. 34, 208 (2005); (c) T. Uemura, S. Kitagawa, Chem. Lett. 34, 132 (2005); (d) B.-H. Ye, M.-Li. Tong, X.-M. Chen, Coord. Chem. Rev. 249, 545 (2005); (e) S. Kitagawa, K. Uemura, Chem. Soc. Rev. 34, 109 (2005); (f) J.-C. Dai, Z.-Y. Fu, X.-T. Wu, in Encyclopedia of Nanoscience and Nanotechnology, vol. 10, ed. by H.S. Nalwa (American Scientific Publishers, Stevenson Ranch, Cal. 2004), p. 247; (g) B. Kesanli, W. Lin, Coord. Chem. Rev. 246, 305 (2003); (h) L. Carlucci, G. Ciani, D.M. Proserpio, Coord. Chem. Rev. 246, 247 (2003); (i) A. Erxleben, Coord. Chem. Rev. 246, 203 (2003); (j) S.-L. Zheng, M.-L. Tong, X.-M. Chen, Coord. Chem. Rev. 246, 185 (2003); (k) S.A. Barnett, N.R. Champness, Coord. Chem. Rev. 246, 145 (2003); (l) A.S. Abd-El-Aziz, E.K. Todd, Coord. Chem. Rev. 246, 3 (2003). (m) S.R. Batten, K.S. Murray, Coord. Chem. Rev. 246, 103 (2003); (n) D. Woehrle, in Metal Complexes and Metals in Macromolecules, ed. by D. Woehrle, A.D. Pomogailo (2003) p. 279Google Scholar
  2. 2.
    (a) Y. Liu, Y. Li, K.S.J. Schan, Photochem. Photobio. C: Photochem. Rev. 3, 1 (2002); (b) P.R. Andres, U.S. Schubert, Adv. Mat. 16, 1043 (2004); (c) D.R. Tyler, Coord. Chem. Rev. 246, 291 (2003); (d) U.S. Schubert, C. Eschbaumer, Angew. Chem. Int. Ed. 41, 2892 (2002)Google Scholar
  3. 3.
    (a) S.L. James, Coord. Chem. Rev. 276, 32 (2003); (b) T. Tanase, Bull. Chem. Soc. Jpn. 75, 1407 (2002); (c) M. Hanack, D. Dini, in Porphyrin Handbook, vol. 18, ed. by K.M. Kadish, K.M. Smith, R. Guilard (Elsevier Science, San Diego, CA 2003), p. 251Google Scholar
  4. 4.
    (a) P.D. Harvey, J. Inorg. Organomet. Polym. 14, 211 (2004); (b) P.D. Harvey, Macromolecule Containing Metal and Metal-like Elements, Chapter 4, vol. 5 (Wiley, New York, 2005), p. 83; (c) P.D. Harvey, Coord. Chem. Rev. 219–221, 17 (2001)Google Scholar
  5. 5.
    (a) P.D. Harvey, Frontiers in Transition Metal-Containing Polymers (Wiley Interscience, John Wiley and Sons Inc., New York, 2007), p. 321; (b) P.D. Harvey, The Spectroscopy and Photophysical Behavior of Diphosphine- and Diisocyanide-Containing Coordination and Organometallic Oligomers and Polymers: Focus on Palladium and Platinum, Copper, Silver, and Gold (Wiley Interscience, John Wiley and Sons Inc., New York, scheduled for 2007)Google Scholar
  6. 6.
    For recent examples see (a) A. Mendia, E. Cerrada, F.J. Arnaiz, M. Laguna, J. Chem. Soc., Dalton Trans. 609 (2006); (b) M. Knorr, G. Schmitt, M.M. Kubicki, E. Vigier, Eur. J. Inorg. Chem. 514 (2003); (c) N. Tsukada, O. Tamura, Y. Inoue, Organometallics, 21, 2521 (2002); (d) D. Evrard, K. Groison, A. Decken, Y. Mugnier, P.D. Harvey, Inorg. Chim. Acta 359, 2608 (2006); (e) D. Evrard, M. Drouin, Y. Mugnier, P.D. Harvey, Inorg. Chim. Acta 350, 442 (2003)Google Scholar
  7. 7.
    D. Evrard, S. Clément, D. Lucas, B. Hanquet, M. Knorr, C. Strohmann, A. Decken, Y. Mugnier, P.D. Harvey, Inorg. Chem. 45, 1305 (2006)CrossRefGoogle Scholar
  8. 8.
    P.G. Pringle, B.L. Shaw, J. Chem. Soc., Dalton Trans. 5, 889 (1983)CrossRefGoogle Scholar
  9. 9.
    N.L. Wagner, K.L. Murphy, D.T. Haworth, D.W. Bennett, Inorganic Syntheses, vol. 34 (Wiley–VCH, 2004), p. 24Google Scholar
  10. 10.
    R.J. Angelici, M.H. Quick, G.A. Kraus, D.T. Plummer, Inorg. Chem. 21, 2178 (1982)CrossRefGoogle Scholar
  11. 11.
    M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople (Gaussian Inc., Wallingford CT, 2004)Google Scholar
  12. 12.
    S. Clément, L. Guyard, M. Knorr, S. Dilsky, C. Strohmann, M. Arroyo, J. Organomet. Chem. 692, 839 (2007)Google Scholar
  13. 13.
    S. Sicard, J.-F. Berubé, D. Samar, A. Messaoudi, D. Fortin, F. Lebrun, J.-F. Fortin, A. Decken, P.D. Harvey, Inorg. Chem. 43, 5321 (2004)CrossRefGoogle Scholar
  14. 14.
    D. Samar, J.-F. Fortin, A. Decken, D. Fortin, P.D. Harvey, J. Inorg. Organomet. Poly. Mat. 15, 411 (2006)CrossRefGoogle Scholar
  15. 15.
    See for example E. Fournier, S. Sicard, A. Decken, P.D. Harvey, Inorg. Chem. 43, 1491 (2004)Google Scholar
  16. 16.
    J.N. Demas, G.A.J. Crosby, Am. Chem. Soc. 93, 2841 (1971)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Sébastien Clément
    • 1
  • Shawkat Mohammed Aly
    • 2
  • Karl Gagnon
    • 2
  • Alaa S. Abd-El-Aziz
    • 3
  • Michael Knorr
    • 1
  • Pierre D. Harvey
    • 2
    Email author
  1. 1.Institut UTINAM UMR CNRS 6213Université de Franche-Comté, Faculté des Sciences et des TechniquesBesanconFrance
  2. 2.Département de ChimieUniversité de SherbrookeSherbrookeCanada
  3. 3.Department of ChemistryUniversity of British ColumbiaKelownaCanada

Personalised recommendations