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Synthesis and Self-Organization of Zinc β-(Dialkoxyphosphoryl)porphyrins in the Solid State and in Solution

Authors

  • Ekaterina V. Vinogradova,

    1. Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Dr. Yulia Y. Enakieva,

    1. Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
    2. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninsky pr., 31, GSP-1, 119991, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Prof. Sergey E. Nefedov,

    1. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninsky pr., 31, GSP-1, 119991, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Dr. Kirill P. Birin,

    1. Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
    2. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninsky pr., 31, GSP-1, 119991, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Prof. Aslan Y. Tsivadze,

    1. Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
    2. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninsky pr., 31, GSP-1, 119991, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Prof. Yulia G. Gorbunova,

    Corresponding author
    1. Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
    2. Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry, Leninsky pr., 31, GSP-1, 119991, Moscow (Russia), Fax: (+7) 495 952-25-66
    • Russian Academy of Sciences, Frumkin Institute of Physical Chemistry and Electrochemistry, Leninsky pr., 31, GSP-1, 119071, Moscow (Russia), Fax: (+7) 495 952-25-66
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  • Dr. Alla G. Bessmertnykh Lemeune,

    1. Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB-UMR CNRS 6302), 9 Avenue Alain Savary-BP 47870, 21078 Dijon Cedex (France)
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  • Dr. Christine Stern,

    1. Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB-UMR CNRS 6302), 9 Avenue Alain Savary-BP 47870, 21078 Dijon Cedex (France)
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  • Prof. Roger Guilard

    Corresponding author
    1. Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB-UMR CNRS 6302), 9 Avenue Alain Savary-BP 47870, 21078 Dijon Cedex (France)
    • Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB-UMR CNRS 6302), 9 Avenue Alain Savary-BP 47870, 21078 Dijon Cedex (France)
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Abstract

The first synthesis and self-organization of zinc β-phosphorylporphyrins in the solid state and in solution are reported. β-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their ZnII complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon–phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-β-(dialkoxyphosphoryl)porphyrins 1 Zn3 Zn starting from the β-bromo-substituted zinc porphyrinate ZnTPPBr (TPP=tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)2 (R=Et, iPr, nBu). The derivatives 1 Zn3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72 % yield. The use of a Pd-catalyzed C[BOND]P bond-forming reaction was further extended to the synthesis of β-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H2TPPBr4 led to the formation of a mixture of the 2,12- and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H2 and 6 H2 in 81 % total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc β-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process.

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