1H NMR法によるピロール環拡張ポルフィリン亜鉛錯体の自己配位挙動解析

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The expanded π-conjugation of porphyrin macrocycles, which are models of chlorophyll, has been intensively explored for the last two decades. Expanded π-conjugated porphyrin macrocycles exhibit structures, electronic properties, coordination chemistry, and reactivities different from those exhibited by other porphyrin macrocycles. The crystal structure of the light-harvesting antenna complex (LH2) from the Rhodopseudomonas acidophila strain 10050 shows that the active assembly consists of two concentric cylinders of helical protein subunits, which enclose the dimeric pigment molecules. Self-assembling into porphyrin arrays through noncovalent bonds is challenging from the viewpoint of nature's synthetic methodology. In this study, the preparation of a pyrrole-fused porphyrin free base attached with ethoxycarbonyl and aldehyde groups at α-pyrrole positions was achieved. It was easy to introduce a zinc metal ion to the pyrrole-fused porphyrin free base by a conventional methodology. Through previous studies, it has become increasingly apparent that pyrrole-fused porphyrin-zinc complexes are very attractive as self-assembling systems. When we increased the solution concentration of the pyrrole-fused porphyrin-zinc complex from 0.5 mM to 6.0 mM, large changes were detected by 1H NMR spectroscopy. The significantly upfield chemical shifts observed for the methylene protons of ethoxycarbonyl and part of porphyrin moiety suggest that pyrrole-fused porphyrin-zinc complexes interact with each other through the zinc metal center and carbonyl oxygen. Calculations to fit the theoretical curves to the observed data of methyl and methylene protons were perfomed, and the K value was obtained by the fitting curves.
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1H NMR法によるピロール環拡張ポルフィリン亜鉛錯体の自己配位挙動解析

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