Self-aggregation of synthetic zinc chlorophyll derivatives possessing multi-perfluoroalkyl chains in perfluorinated solvents.
Zinc 3(1)-hydroxy-13(1)-oxo-chlorins possessing two, three, four and six perfluorooctyl chains were synthesized from naturally occurring chlorophyll-a. Only the synthetic zinc chlorin possessing six perfluorooctyl chains was directly dissolved in perfluorinated solvents due to its high fluorine content in molecular weight (over 50%). In this solution, visible absorption spectra gave a red-shifted Q(y) band at 723 nm (compared to 648 nm in THF) and showed the formation of well-ordered self-aggregates. No monomeric form was observed in the solution from any fluorescence emission spectra from visible absorption spectra. In the aggregate solution, no precipitation occurred during either standing for a long period or heating at 70 degrees C. This showed that the supramolecular structure was stabilized by F-F interactions on its surface among the perfluorooctyl chains on the 17-position and perfluorinated solvents. The core part of the supramolecular structure was constructed by a special intramolecular bond of Zn ... O3(2)-H ... O=C13(1), which was confirmed from resonance Raman spectral analysis.
Shibata
Reiko
R
Department of Bioscience and Biotechnology, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga, Japan.
Mizoguchi
Tadashi
T
Inazu
Toshiyuki
T
Tamiaki
Hitoshi
H
D002734:Chlorophyll / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013055:Spectrophotometry, Infrared; D015032:Zinc / Q000737:chemistry*
D012997:Solvents; D002734:Chlorophyll; D015032:Zinc