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Research on Chemical Intermediates

, Volume 39, Issue 1, pp 221–232 | Cite as

Metallation of a cyclic chlorophyll hetero-dyad, and the optical properties of synthetic metallo-dyads

  • Hitoshi Tamiaki
  • Nobuo Kosaka
  • Yusuke Kinoshita
Article

Abstract

A cyclic chlorophyll hetero-dyad 1-H2H2, prepared by double ester linking of two structurally different pyropheophorbide-a moieties through 3-CH2OCO-132′ and 172-COOCH2-3′, was metallated with zinc and copper to give mono and di-metallated complexes 1-MH2 or 1-H2M and 1-MM. The metallation proceeded stepwise and regioselectively, with predominant synthesis of one of the two mono-metallated complexes 1-MH2 as intermediate. The di-zinc complex produced, 1-ZnZn, was demetallated exclusively via the same mono-zinc complex 1-ZnH2 as was the major intermediate during metallation. Visible and/or circular dichroism spectra of 1-H2H2, 1-MH2, 1-H2M, and 1-MM (M = Ni, Cu, or Zn) were measured in organic solvents. Intramolecular interaction of chlorin chromophores is discussed and compared with that of the corresponding monomeric species.

Keywords

Chlorophyll Dimer Intramolecular interaction Metal complex Regioisomer 

Notes

Acknowledgments

We thank Dr Toru Oba of Utsunomiya University for useful discussion. This work was partially supported by a Grant-in-Aid for Scientific Research (A) (No. 22245030) from the Japan Society for the Promotion of Science (JSPS).

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Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Hitoshi Tamiaki
    • 1
  • Nobuo Kosaka
    • 1
  • Yusuke Kinoshita
    • 1
  1. 1.Department of Bioscience and BiotechnologyFaculty of Science and Engineering, Ritsumeikan UniversityKusatsuJapan

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