Synthesis and Photophysical Properties of Fullerene–Phthalocyanine–Porphyrin Triads and Pentads

Authors

  • Dr. Roger F. Enes,

    1. Departamento de Química e QOPNA, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro (Portugal)
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  • Dr. Juan-José Cid,

    1. Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 91 497 3966
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  • Anita Hausmann,

    1. Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), University of Erlangen-Nuremberg, Egerlandstraße 3, 91058 Erlangen (Germany), Fax: (+49) 9131-852-8307
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  • Olga Trukhina,

    1. Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 91 497 3966
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  • Dr. Andreas Gouloumis,

    1. Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040-Madrid (Spain)
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  • Prof. Purificación Vázquez,

    1. Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 91 497 3966
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  • Prof. José A. S. Cavaleiro,

    1. Departamento de Química e QOPNA, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro (Portugal)
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  • Prof. Augusto C. Tomé,

    Corresponding author
    1. Departamento de Química e QOPNA, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro (Portugal)
    • Departamento de Química e QOPNA, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro (Portugal)
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  • Prof. Dirk M. Guldi,

    Corresponding author
    1. Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), University of Erlangen-Nuremberg, Egerlandstraße 3, 91058 Erlangen (Germany), Fax: (+49) 9131-852-8307
    • Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), University of Erlangen-Nuremberg, Egerlandstraße 3, 91058 Erlangen (Germany), Fax: (+49) 9131-852-8307
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  • Prof. Tomás Torres

    Corresponding author
    1. Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 91 497 3966
    2. IMDEA-Nanociencia, Facultad de Ciencias, 28049-Madrid (Spain)
    • Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (Spain), Fax: (+34) 91 497 3966
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Abstract

The synthesis and photophysical properties of several fullerene–phthalocyanine–porphyrin triads (13) and pentads (46) are described. The three photoactive moieties were covalently connected in an one-step synthesis through 1,3-dipolar cycloaddition to C60 of the corresponding azomethine ylides generated in situ by condensation reaction of a substituted N-porphyrinylmethylglycine derivative and an appropriated formyl phthalocyanine or a diformyl phthalocyanine derivative, respectively. ZnP-C60-ZnPc (3), (ZnP)2-ZnPc-(C60)2 (6), and (H2P)2-ZnPc-(C60)2 (5) give rise upon excitation of their ZnP or H2P components to a sequence of energy and charge-transfer reactions with, however, fundamentally different outcomes. With (ZnP)2-ZnPc-(C60)2 (6) the major pathway is an highly exothermic charge transfer to afford (ZnP)(ZnP.+)-ZnPc-(C60.−)(C60). The lower singlet excited state energy of H2P (i.e., ca. 0.2 eV) and likewise its more anodic oxidation (i.e., ca. 0.2 V) renders the direct charge transfer in (H2P)2-ZnPc-(C60)2 (5) not competitive. Instead, a transduction of singlet excited state energy prevails to form the ZnPc singlet excited state. This triggers then an intramolecular charge transfer reaction to form exclusively (H2P)2-ZnPc.+-(C60.−)(C60). A similar sequence is found for ZnP-C60-ZnPc (3).

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