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Synthesis, Characterization and Photophysical Studies of Luminescent Dinuclear and Trinuclear Copper(I) Alkynyl Phosphines

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Abstract

Luminescent polynuclear copper(I) alkynyl complexes, including two trinuclear bicapped complexes, [Cu3(μ-dppm)3(μ 3-η 1-C≡CC6H n4 C4H9)2]BF4 (1) and [Cu3(μ-dppm)3(μ 3-η 1-C≡CC6H4C≡CC6H5)2]BF4 (2), as well as two dinuclear complexes, [Cu2(PPh2Me)4(μ 2-η 1-C≡CC6H n4 C4H9)2] (3) and [Cu2(PPh2Me)4(μ 2-η 1-C≡CC6H4C≡CC6H5)2] (4), have been successfully synthesized and characterized. The carbazole moiety has also been incorporated into the alkynyl skeleton to prepare the trinuclear bicapped complex, [Cu3(μ-dppm)3(μ 3-η 1-C≡CC6H4-Cz)2]BF4 (Cz = carbazole) (5). The crystal structure of 3 has also been determined. The complexes exhibit high-energy intraligand (IL) π → π* absorption bands typical of the corresponding phosphine and alkynyl ligands. The complexes show intense luminescence originated from a 3LMCT [RC≡C− → Cu n ] state (n = 2, 3), with mixing of a triplet metal cluster-centered ds/dp state.

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References

  1. A. Johnson, R. J. Puddephatt, J. M. Quirk (1972). J. Chem. Soc., Chem. Commun. 938.

  2. A. Johnson, R. J. Puddephatt (1977). J. Chem. Soc., Dalton Trans. 1384.

  3. S. Komiya, S. Ozaki, A. Schibue (1986). J. Chem. Soc., Chem. Commun. 1555.

  4. M. J. Irwin, J. J. Vittal, and R. J. Puddephatt (1997). Organometallics 16, 3541.

    Article  CAS  Google Scholar 

  5. O. Schuster, R. Y. Liau, A. Schier, and H. Schmidbaur (2005). Inorg. Chim. Acta 358, 1429.

    Article  CAS  Google Scholar 

  6. O. Schuster and H. Schmidbaur (2005). Organometallics 24, 2289.

    Article  CAS  Google Scholar 

  7. L. A. Méndaz, J. Jiménez, E. Cerrada, F. Mohr, and M. Laguna (2005). J. Am. Chem. Soc. 127, 852.

    Article  Google Scholar 

  8. T. E. Müller, S. W.-K. Choi, D. M. P. Mingos, D. Murphy, D. J. Williams, and V. W.-W. Yam (1994). J. Organomet. Chem. 484, 209.

    Article  Google Scholar 

  9. C.-M. Che, H.-K. Yip, W.-C. Lo, and S.-M. Peng (1994). Polyhedron 13, 887.

    Article  CAS  Google Scholar 

  10. V. W.-W. Yam, W. K.-M. Fung, and K.-K. Cheung (1997). Organometallics 16, 2032.

    Article  CAS  Google Scholar 

  11. O. M. Abu-Salah, A. R. A. Al-Ohaly (1988). J. Chem. Soc., Dalton Trans. 2297.

  12. M. S. Hussain, M. Ul-Haque, and O. M. Abu-Salah (1996). J. Cluster Sci. 7, 167.

    Article  CAS  Google Scholar 

  13. O. Schuster, U. Monkowius, H. Schmidbaur, R. S. Ray, S. Krüger, and N. Rösch (2006). Organometallics 25, 1004.

    Article  CAS  Google Scholar 

  14. S.-K. Yip, C.-L. Chan, W. H. Lam, K.-K. Cheung, and V. W.-W. Yam (2007). Photochem. Photobiol. Sci. 6, 365.

    Article  CAS  Google Scholar 

  15. P. Espinet, J. Forniés, F. Martinez, M. Tomás, E. Lalinde, M. T. Moreno, A. Ruíz, A. J. Welch (1990). J. Chem. Soc. Dalton Trans. 791.

  16. J. Forniés, E. Lalinde, A. Martín, and M. T. Moreno (1995). J. Organomet. Chem. 490, 179.

    Article  Google Scholar 

  17. J. C. Limaa and L. Rodríguez (2011). Chem. Soc. Rev. 40, 5442.

    Article  Google Scholar 

  18. J. Gil-Rubio, V. Cámara, D. Bautista, and J. Vicente (2012). Organometallics 31, 5414.

    Article  CAS  Google Scholar 

  19. I. O. Koshevoy, L. Koskinen, M. Haukka, S. P. Tunik, P. Y. Serdobintsev, A. S. Melnikov, and T. A. Pakkanen (2008). Angew. Chem. Int. Ed. 47, 3942.

    Article  CAS  Google Scholar 

  20. I. O. Koshevoy, A. J. Karttunen, S. P. Tunik, A. Haukka, S. I. Selivanov, A. S. Melnikov, P. Y. Serdobintsev, M. A. Khodorkovskly, and T. A. Pakkanen (2008). Inorg. Chem. 47, 9478.

    Article  CAS  Google Scholar 

  21. I. O. Koshevoy, A. J. Karttunen, S. P. Tunik, M. Haukka, S. I. Selivanov, A. S. Melnikov, P. Y. Serdobintsev, and T. A. Pakkanen (2009). Organometallics 28, 1369.

    Article  CAS  Google Scholar 

  22. I. O. Koshevoy, A. J. Karrtunen, Y.-C. Lin, C.-C. Lin, P.-T. Chou, S. P. Tunik, M. Haukka, and T. A. Pakkanen (2010). Dalton Trans. 39, 2395.

    Article  CAS  Google Scholar 

  23. J. R. Shakirova, E. V. Grachova, V. V. Gurzhiy, I. O. Koshevoy, A. S. Melnikov, O. V. Sizova, S. P. Tunik, and A. Laguna (2012). Dalton Trans. 41, 2941.

    Article  CAS  Google Scholar 

  24. I. S. Krytchankou, D. V. Krupenya, V. V. Gurzhiy, A. A. Belyaev, A. J. Karttunen, I. O. Koshevoy, A. S. Melnikov, and S. P. Tunik (2013). J. Organomet. Chem. 723, 65.

    Article  CAS  Google Scholar 

  25. W.-Y. Wong (2007). Dalton Trans. 4495.

  26. W.-Y. Wong and C.-L. Ho (2006). Coord. Chem. Rev. 250, 2627.

    Article  CAS  Google Scholar 

  27. W.-Y. Wong (2005). Comments Inorg. Chem. 26, 39.

    Article  CAS  Google Scholar 

  28. C. K. Ryu, M. Vitale, and P. C. Ford (1993). Inorg. Chem. 32, 869.

    Article  CAS  Google Scholar 

  29. K. R. Kyle, C. K. Ryu, J. A. DiBenedeo, and P. C. Ford (1991). J. Am. Chem. Soc. 113, 2954.

    Article  CAS  Google Scholar 

  30. K. R. Kyle and P. C. Ford (1989). J. Am. Chem. Soc. 111, 5005.

    Article  CAS  Google Scholar 

  31. A. Vogler, H. Kunkely (1990). J. Am. Chem. Soc., Chem. Commun. 1204.

  32. P. C. Ford and A. Vogler (1993). Acc. Chem. Res. 26, 220.

    Article  CAS  Google Scholar 

  33. P. Pyykkö (1988). Chem. Rev. 88, 563.

    Article  Google Scholar 

  34. P. Pyykkö (1997). Chem. Rev. 97, 597.

    Article  Google Scholar 

  35. P. Pyykkö, J. Li, and N. Runeberg (1994). Chem. Phys. Lett. 218, 133.

    Article  Google Scholar 

  36. H. Schmidbaur (1975). Acc. Chem. Res. 8, 62.

    Article  CAS  Google Scholar 

  37. H. Schmidbaur (1976). Angew. Chem. Int. Ed. Engl. 15, 728.

    Article  Google Scholar 

  38. H. Schmidbaur and A. Schiera (2012). Chem. Soc. Rev. 41, 370.

    Article  CAS  Google Scholar 

  39. W.-Y. Wong (2007). Coord. Chem. Rev. 251, 2400.

    Article  CAS  Google Scholar 

  40. W.-Y. Wong, L. Liu, and J.-X. Shi (2003). Angew. Chem. Int. Ed. 42, 4064.

    Article  CAS  Google Scholar 

  41. L. Naldini, F. Demartin, M. Manassero, M. Sansoni, G. Rassu, and M. A. Zoroddu (1985). J. Organomet. Chem. 279, c42.

    Article  CAS  Google Scholar 

  42. M. P. Gamasa, J. Gimeno, E. Lastra, A. Aguirre, and S. García-Granda (1989). J. Organomet. Chem. 378, C11.

    Article  CAS  Google Scholar 

  43. J. Diéz, M. P. Gamasa, J. Gimeno, A. Aguirre, and S. García-Granda (1991). Organometallics 10, 380.

    Article  Google Scholar 

  44. J. Diéz, M. P. Gamasa, J. Gimeno, E. Lastra, A. Aguirre, and S. García-Granda (1993). Organometallics 12, 2213.

    Article  Google Scholar 

  45. V. W.-W. Yam, W.-K. Lee, and T.-F. Lai (1993). Organometallics 12, 2383.

    Article  CAS  Google Scholar 

  46. V. W.-W. Yam, W.-K. Lee, K.-K. Cheung (1996). J. Chem. Soc., Dalton Trans. 2335.

  47. V. W.-W. Yam, S. W.-K. Choi, C.-L. Chan, K.-K. Cheung, Chem. Commun. 2067.

  48. V. W.-W. Yam, W. K.-M. Fung, and M.-T. Wong (1997). Organometallics 16, 1772.

    Article  CAS  Google Scholar 

  49. V. W.-W. Yam, W. K.-M. Fung, and K.-K. Cheung (1996). Angew. Chem. Int. Ed. Engl. 35, 1100.

    Article  CAS  Google Scholar 

  50. V. W.-W. Yam, W. K.-M. Fung, and K.-K. Cheung (1999). J. Cluster Sci. 10, 37.

    Article  CAS  Google Scholar 

  51. T. C. Higgs, P. J. Bailey, S. Parsons, and P. A. Tasker (2002). Angew. Chem. Int. Ed. 41, 3038.

    Article  CAS  Google Scholar 

  52. C. W. Baxter, T. C. Higgs, P. J. Bailey, S. Parsons, F. McLachlan, M. McPartlin, and P. A. Tasker (2006). Chem. Eur. J. 12, 6166.

    Article  CAS  Google Scholar 

  53. C.-L. Chan, K.-L. Cheung, W. H. Lam, E. C.-C. Cheng, N. Zhu, S. W.-K. Choi, and V. W.-W. Yam (2006). Chem. Asian J. 1, 273.

    Article  CAS  Google Scholar 

  54. X. He, N. Zhu, and V. W.-W. Yam (2011). Dalton Trans. 40, 9703.

    Article  CAS  Google Scholar 

  55. H. D. De Ahna and H. D. Hardt (1972). Z. Anorg. Allg. Chem. 387, 61.

    Article  Google Scholar 

  56. H. D. Hardt and H. Gechnizdjani (1973). Z. Anorg. Allg. Chem. 397, 23.

    Article  CAS  Google Scholar 

  57. H. D. Hardt and A. Pierre (1973). Z. Anorg. Allg. Chem. 402, 107.

    Article  CAS  Google Scholar 

  58. H. D. Hardt and A. Pierre (1977). Inorg. Chim. Acta 25, L59.

    Article  CAS  Google Scholar 

  59. V. W.-W. Yam and K. K.-W. Lo (1999). Chem. Soc. Rev. 28, 323.

    Article  CAS  Google Scholar 

  60. G. F. Manbeck, W. W. Brennessel, R. A. Stockland Jr, and R. Eisenberg (2010). J. Am. Chem. Soc. 132, 12307.

    Article  CAS  Google Scholar 

  61. P. Alemany and S. Alvarez (1992). Inorg. Chem. 31, 4266.

    Article  CAS  Google Scholar 

  62. B. Morosin and J. Howatson (1971). J. Organomet. Chem. 29, 7.

    Article  CAS  Google Scholar 

  63. G. D. Stucky, A. M. McPherson, W. E. Rhine, J. J. Eisch, and J. L. Considine (1974). J. Am. Chem. Soc. 96, 1941.

    Article  CAS  Google Scholar 

  64. A. Almenningen, L. Fernholt, and A. Haaland (1978). J. Organomet. Chem. 155, 245.

    Article  CAS  Google Scholar 

  65. S. B. Harkins and J. C. Peters (2004). J. Am. Chem. Soc. 126, 2885.

    Article  CAS  Google Scholar 

  66. S. B. Harkins and J. C. Peters (2005). J. Am. Chem. Soc. 127, 2030.

    Article  CAS  Google Scholar 

  67. N. P. Mankad, E. Rivard, S. B. Harkins, and J. C. Peters (2005). J. Am. Chem. Soc. 127, 16032.

    Article  CAS  Google Scholar 

  68. J. C. Deaton, S. C. Switalski, D. Y. Kondakov, R. H. Young, T. D. Pawlik, D. J. Giesen, S. B. Harkins, A. J. M. Miller, S. F. Mickenberg, and J. C. Peters (2010). J. Am. Chem. Soc. 132, 9499.

    Article  CAS  Google Scholar 

  69. K. Hiraki, Y. Fuchita, and Y. Morita (1978). Bull. Chem. Soc. Jpn. 51, 2012.

    Article  CAS  Google Scholar 

  70. G. Hattori, K. Sakata, H. Matsuzawa, Y. Tanabe, Y. Miyake, and Y. Nishibayashi (2010). J. Am. Chem. Soc. 132, 10592.

    Article  CAS  Google Scholar 

  71. S. Y. De Boer, Y. Gloaguen, M. Lutz, and J. I. van der Vlugt (2012). Inorg. Chim. Acta 380, 336.

    Article  Google Scholar 

  72. V. Pawlowski, G. Knör, C. Lennartz, A. Vogler (2005). Eur. J. Inorg. Chem. 3167.

  73. M. I. Bruce, N. N. Zaitseva, B. W. Skelton, N. Somers, and A. H. White (2007). Inorg. Chim. Acta 360, 681.

    Article  CAS  Google Scholar 

  74. H. Nishihare, T. Shimura, A. Ohkubo, N. Matsuda, and K. Aramaki (1993). Adv. Mater. 5, 752.

    Article  Google Scholar 

  75. K. Li, Q. Wang (2005). Chem. Commun. 4786.

  76. SHELXS 97: G. M. Sheldrick, SHELXS 97: Programs for Crystal Structure Analysis, release 97–22; University of Göttingen: Göttingen, Germany, 1997.

  77. V. W.-W. Yam, W.-K. Lee, K.-K. Cheung, H.-K. Lee, W.-P. Leung (1996). J. Chem. Soc. Dalton Trans. 2889.

  78. R. I. Papasergio, C. L. Raston, A. H. White (1983). J. Chem. Soc., Chem. Commun. 1419.

  79. W.-Y. Wong (2005). Coord. Chem. Rev. 249, 971.

    Article  CAS  Google Scholar 

  80. G. T. Dalton, M. P. Cifuentes, L. A. Watson, S. Petrie, R. Stranger, M. Samoc, and M. G. Humphrey (2009). Inorg. Chem. 48, 6534.

    Article  CAS  Google Scholar 

  81. E. Payet, A. Auffrant, X. F. Le Goff, and P. Le Floch (2010). J. Organomet. Chem. 695, 1499.

    Article  CAS  Google Scholar 

  82. M. I. Bruce (1986). Pure Appl. Chem. 58, 553.

    Article  CAS  Google Scholar 

  83. M. I. Bruce (1990). Pure Appl. Chem. 62, 1021.

    Article  CAS  Google Scholar 

  84. A. J. Edwards, M. A. Paver, P. A. Raithby, M. A. Rennie, C. A. Russell, and D. S. Wright (1994). Organometallics 13, 4967.

    Article  CAS  Google Scholar 

  85. G. van Koten, S. L. James and J. T. B. H. Jastrzebski in E. W. Abel, F. G. A. Stone and G. Wilkinson (eds.), Comprehensive Organometallic Chemistry II (Pergamon, Oxford, 1995), Vol. 3, p. 75.

  86. B. J. Hathaway, in G. Wilkinson, R. D. Gillard and J. A. McCleverty (eds.), Comprehensive Coordination Chemistry (Pergamon, Oxford, 1987), Vol. 5, p. 533.

  87. R. J. Lancashire, in G. Wilkinson, R. D. Gillard and J. A. McCleverty (eds.), Comprehensive Coordination Chemistry (Pergamon, Oxford, 1987), Vol. 5, p. 775.

  88. R. J. Puddephatt, in G. Wilkinson, R. D. Gillard, J. A. McCleverty (eds.), Comprehensive Coordination Chemistry (Pergamon, Oxford, 1987), Vol. 5, p. 861.

  89. V. W.-W. Yam, K. K.-W. Lo, W. K.-M. Fung, and C. R. Wang (1998). Coord. Chem. Rev. 171, 17.

    Article  CAS  Google Scholar 

  90. V. W.-W. Yam and K. M.-C. Wong (2005). Top. Curr. Chem. 257, 1.

    Article  CAS  Google Scholar 

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Acknowledgments

V.W.-W.Y. acknowledges support from the University Grants Committee Areas of Excellence Scheme (AoE/P-03/08) and the URC Strategic Research Theme on New Materials. This work has been supported by the ANR-RGC Joint Research Scheme sponsored by the Research Grants Council of Hong Kong and the French National Research Agency (Agence Nationale de la Recherche, ANR) (A-HKU 704/12). S.K.-L.S. acknowledges the receipt of a postgraduate studentship and a University Postgraduate Fellowship, both administered by The University of Hong Kong. V.K.-M.A. acknowledges the receipt of a postdoctoral fellowship administered by The University of Hong Kong. Dr. K.M. Ng at The University of Hong Kong is acknowledged for his helpful technical assistance in the HR-ESI–MS characterization.

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  1. Institute of Molecular Functional Materials [Areas of Excellence Scheme, University Grants Committee (Hong Kong)], and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, People’s Republic of China

    Steven Kin-Lok Siu, Vonika Ka-Man Au & Vivian Wing-Wah Yam

  2. Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, People’s Republic of China

    Chi-Chiu Ko

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Siu, S.KL., Ko, CC., Au, V.KM. et al. Synthesis, Characterization and Photophysical Studies of Luminescent Dinuclear and Trinuclear Copper(I) Alkynyl Phosphines. J Clust Sci 25, 287–300 (2014). https://doi.org/10.1007/s10876-013-0648-2

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