Peripheral Arylation of Subporphyrazines

Authors

  • Tomohiro Higashino,

    1. Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966
    2. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
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  • Dr. M. Salomé Rodríguez-Morgade,

    Corresponding author
    1. Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966
    • M. Salomé Rodríguez-Morgade, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

      Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970

      Tomás Torres, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

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  • Prof. Dr. Atsuhiro Osuka,

    Corresponding author
    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970
    • M. Salomé Rodríguez-Morgade, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

      Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970

      Tomás Torres, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

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  • Prof. Tomás Torres

    Corresponding author
    1. Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966
    2. IMDEA-Nanociencia, c/Faraday, 9, Campus de Cantoblanco, 28049 Madrid (Spain)
    • M. Salomé Rodríguez-Morgade, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

      Atsuhiro Osuka, Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3970

      Tomás Torres, Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain), Fax: (+34) 914973966

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Abstract

Peripherally hexaarylated subporphyrazines (SubPzs) have been prepared through a Pd-catalyzed, CuTC-mediated coupling of a hexaethylsulfanylated subporphyrazine with arylboronic acids. The introduced aryl substituents strongly influence the electronic properties of the subporphyrazine through effective conjugative interaction. Aryl rings endowed with π-electron-donating groups at the para positions produce a remarkable perturbation of the electron density of the SubPz macrocycle. This is reflected through significant redshifts of the SubPz CT and Q-bands, together with increase of the molar absorptivity of the former, with respect to those exhibited by the hexaphenyl-SubPz 2 a. Moreover, the trend in the first SubPz reduction potentials correlates with the Hammett constants (σp) corresponding to the para substituents of the aryl. The domed, extended SubPz π-system self-assembles in the solid state to form a dimeric capsule that houses a solvent molecule.

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