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.
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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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Tamiaki, H., Kosaka, N. & Kinoshita, Y. Metallation of a cyclic chlorophyll hetero-dyad, and the optical properties of synthetic metallo-dyads. Res Chem Intermed 39, 221–232 (2013). https://doi.org/10.1007/s11164-012-0644-4
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DOI: https://doi.org/10.1007/s11164-012-0644-4