Download PDF
Synlett 2006(19): 3231-3236  
DOI: 10.1055/s-2006-951547
LETTER
© Georg Thieme Verlag Stuttgart · New York

First Synthesis of Symmetrical and Unsymmetrical Conjugated Trinuclear Phthalocyanines Covalently Linked by Ethynyl Bridges

Eva M. García-Frutos, David D. Díaz, Purificación Vázquez*, Tomás Torres*
Departamento de Química Orgánica (C-I), Universidad Autónoma de Madrid, Cantoblanco 28049 Madrid, Spain
Fax: +34(91)3973966; e-Mail: tomas.torres@uam.es;
Further Information

Publication History

Received 28 August 2006
Publication Date:
23 November 2006 (online)

    Permissions and Reprints All articles of this category

Abstract

For the first time, symmetrical and unsymmetrical π-electron-conjugated trinuclear phthalocyanines (Pcs) were syn­thesized with the Pc units connected directly by ethynyl linkages. Symmetrically alkoxy-substituted bridged ethynylphthalocyaninatozinc(II) triad was prepared by direct Sonogashira cross-coupling reaction between suitable diiodo Pc and alkynyl Pc derivatives. Nevertheless, the synthesis of the Pc-based triad having a donor-­acceptor electron character was carried out by means of co-cyclo­tetramerization of two different phthalonitriles, namely 4,5-bis(propylsulfonyl)phthalonitrile and 4,5-[hexa(butoxy)ethynylphthalo-cyaninatozinc(II)]phthalonitrile in the presence of a cobalt(II) salt.

Key words

phthalocyanines - triad - ethynyl - Sonogashira reaction

    References

  • 1a Yang SI. Li J. Cho HS. Kim D. Bocian DF. Holten D. Lindsey JS. J. Mater. Chem.  2000,  10:  283 
    CrossrefGoogle Scholar
  • 1b Miller MA. Lammi RK. Prathapan S. Holten D. Lindsey JS. J. Org. Chem.  2000,  65:  6634 
    CrossrefGoogle Scholar
  • 1c Yeow EKL. Ghiggino KP. Reek JNH. Crossley MJ. Bosman AW. Schenning APHJ. Meijer EW. J. Phys. Chem. B  2000,  104:  2596 
    CrossrefGoogle Scholar
  • 1d Guldi DM. Gouloumis A. Vázquez P. Torres T. Georgakilas V. Prato M. J. Am. Chem. Soc.  2005,  127:  5811 
    CrossrefGoogle Scholar
  • 1e de la Escosura A. Martínez-Díaz MV. Guldi DM. Torres T. J. Am. Chem. Soc.  2006,  128:  4112 
    CrossrefGoogle Scholar
  • 1f González-Rodríguez D. Torres T. Olmstead MM. Rivera J. Herranz MA. Echegoyen L. Atienza-Castellanos C. Guldi DM. J. Am. Chem. Soc.  2006,  128:  10680 
    CrossrefGoogle Scholar
  • 2a Li D. Ratner MA. Marks TJ. J. Am. Chem. Soc.  1988,  110:  1707 
    CrossrefGoogle Scholar
  • 2b de la Torre G. Vázquez P. Agulló-López F. Torres T. J. Mater. Chem.  1998,  8:  1671 
    CrossrefGoogle Scholar
  • 2c de la Torre G. Vázquez P. Agulló-López F. Torres T. Chem. Rev.  2004,  104:  3723 
    CrossrefGoogle Scholar
  • 2d O’Flaherty SM. Hold SV. Cook MJ. Torres T. Chen Y. Hanack M. Blau WJ. Adv. Mater.  2003,  15:  19 
    CrossrefGoogle Scholar
  • 3a Sastre A. del Rey B. Torres T. J. Org. Chem.  1996,  61:  8591 
    CrossrefGoogle Scholar
  • 3b Sastre A. Díaz-García MA. del Rey B. Dhenaut C. Zyss J. Ledoux I. Agulló-López F. Torres T. J. Phys. Chem. A  1997,  101:  9773 
    CrossrefGoogle Scholar
  • 3c Tian M. Wada T. Kimura-Suda H. Sasabe H. J. Mater. Chem.  1997,  7:  861 
    CrossrefGoogle Scholar
  • 3d Sastre A. Torres T. Hanack M. Tetrahedron Lett.  1995,  36:  8501 
    CrossrefGoogle Scholar
  • 3e Cabezón B. Rodríguez-Morgade S. Torres T. J. Org. Chem.  1995,  60:  1872 
    CrossrefGoogle Scholar
  • 3f de la Torre G. Martínez-Díaz MV. Ashton PR. Torres T. J. Org. Chem.  1998,  63:  8888 
    CrossrefGoogle Scholar
  • 3g Calvete MJF. Dini D. Flom SR. Hanack M. Pong RGS. Shirk JS. Eur. J. Org. Chem.  2005,  3499 
    CrossrefGoogle Scholar
  • 4a Rojo G. de la Torre G. García-Ruiz J. Ledoux I. Torres T. Zyss J. Agulló-López F. Chem. Phys.  1999,  245:  27 
    Google Scholar
  • 4b Maya EM. Vázquez P. Torres T. Chem. Eur. J.  1999,  5:  2004 
    Google Scholar
  • 5 Maya EM. Vázquez P. Torres T. Chem. Commun.  1997,  1175 
    CrossrefGoogle Scholar
  • 6 Maya EM. Vázquez P. Torres T. Gobbi L. Diederich F. Pyo S. Echegoyen L. J. Org. Chem.  2000,  65:  823 
    CrossrefGoogle Scholar
  • 7a Maya EM. García C. García-Frutos EM. Vázquez P. Torres T. J. Org. Chem.  2000,  65:  2733 
    CrossrefGoogle Scholar
  • 7b Maya EM. García-Frutos EM. Vázquez P. Torres T. Martín G. Rojo G. Agulló-López F. González-Jonte RH. Ferro VR. García de la Vega JM. Ledoux I. Zyss J. J. Phys. Chem. A  2003,  107:  2110 
    CrossrefGoogle Scholar
  • 8 González-Cabello A. Vázquez P. Torres T. Guldi DM. J. Org. Chem.  2003,  68:  8635 
    CrossrefGoogle Scholar
  • 9 For a recent review on the synthesis of alkynyl-substituted Pcs, see: Bottari G. Díaz DD. Torres T. J. Porphyrins Phthalocyanines  2006,  in press 
    Google Scholar
  • 10 de la Torre G. Gouloumis A. Vázquez P. Torres T. Angew. Chem. Int. Ed.  2001,  40:  2895 
    CrossrefGoogle Scholar
  • 11 Kalkan A. Koca A. Bayir ZA. Polyhedron  2004,  23:  3155 
    CrossrefGoogle Scholar
  • 12 Poon KW. Liu W. Chan PK. Yang Q. Chan TWD. Mak TCW. Ng DKP. J. Org. Chem.  2001,  66:  1553 
    CrossrefGoogle Scholar
  • 13 Leznoff CC. Li Z. Isago H. D’Ascanio AM. Terekhov DS. J. Porphyrins Phthalocyanines  1999,  3:  406 
    CrossrefGoogle Scholar
  • 14a Blum J. Baidossi W. Badrieh Y. Hoffmann RE. Schumann H. J. Org. Chem.  1995,  60:  4738 
    CrossrefGoogle Scholar
  • 14b Schreiner PR. Prall M. Lutz V. Angew. Chem. Int. Ed.  2003,  42:  5757 
    CrossrefGoogle Scholar
  • 14c Kovalenko SV. Peabody S. Manoharan M. Clark RJ. Alabugin IV. Org. Lett.  2004,  6:  2457 
    CrossrefGoogle Scholar
  • 15 García-Frutos EM. Fernández-Lázaro F. Maya EM. Vázquez P. Torres T. J. Org. Chem.  2000,  65:  6841 
    CrossrefGoogle Scholar
  • 16 Berera R. Herrer C. van Stokkum IHM. Vengris M. Kodis G. Palacios RE. van Amerongen H. van Grondelle R. Gust D. Moore TA. Moore AL. Kennis JTM. Proc. Natl. Acad. Sci. U.S.A.  2006,  103:  5343 
    CrossrefGoogle Scholar
  • 17 Marcuccio SM. Svirskaya PI. Greenberg S. Lever ABP. Leznoff CC. Tomer KB. Can. J. Chem.  1985,  63:  3057 
    CrossrefGoogle Scholar