Synthesis, structures, and properties of meso-phosphorylporphyrins: Self-organization through P-oxo-zinc coordination

Yoshihiro Matano, Kazuaki Matsumoto, Yukiko Terasaka, Hiroki Hotta, Yasuyuki Araki, Osamu Ito, Motoo Shiro, Takahiro Sasamori, Norihiro Tokitoh, Hiroshi Imahori

研究成果: Article査読

63 被引用数 (Scopus)

抄録

The synthesis, structures, and optical and electrochemical properties of meso-phosphorylporphyrins are described. The copper-catalyzed carbon-phosphorus cross-coupling reaction of a meso-iodoporphyrin with di-n-butyl phosphite and diphenylphosphane oxide has proved to be an efficient and general method for the synthesis of meso-phosphorylporphyrins. Zinc phosphorylporphyrins thus obtained readily undergo self-organization through Poxo-Zn coordination to form noncovalently linked, cofacial porphyrin dimers or linear oligomers, which have been characterized by spectroscopic methods and X-ray crystallographic analyses. In toluene, CH2Cl2, and CHCl3, the zinc phosphorylporphyrins exist mostly as dimers or monomers, depending on their concentrations, the temperature, and the presence of additives. The self-association constants for dimerization in toluene have been determined by UV/Vis absorption titration measurements. The meso-diphenylphosphorylporphyrin dimer displays excitonic coupling of the Soret band with a splitting energy of 940 cm-1. Fluorescence lifetimes of the zinc phosphorylporphyrins have been found to be affected only slightly by the concentration of the solution, and by the addition of triphenylphosphane oxide, suggesting that the effect of dimerization on their photodynamics in the Si state is negligible. On the other hand, the effect of dimerization is clearly reflected in their electrochemical oxidation processes, as the initially produced radical cations are efficiently delocalized over the two porphyrin rings. These findings demonstrate the potential utility of meso-phosphorylporphyrins as new models for the special pair in photosynthesis and as new building blocks for porphyrin-based supramolecular materials.

本文言語English
ページ(範囲)891-901
ページ数11
ジャーナルChemistry - A European Journal
13
3
DOI
出版ステータスPublished - 2007 1 30

ASJC Scopus subject areas

  • 触媒
  • 化学 (全般)
  • 有機化学

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