| Budget Amount *help |
¥3,276,000 (Direct Cost: ¥2,520,000、Indirect Cost: ¥756,000)
Fiscal Year 2009: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2008: ¥1,716,000 (Direct Cost: ¥1,320,000、Indirect Cost: ¥396,000)
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| Research Abstract |
Synthesis of novel porphyrinoids aimed at development of nonlinear optical materials or photodynamic therapy medicines had been started. At first, since unpredictable synthetic problems were found during the synthesis of oligo-pyrrole precursors according to the reported procedure, the reaction conditions were modified so that formation of byproducts was suppressed. In addition, a rare oligo-pyrrole unit bearing a pyridine ring that was difficult to introduce so far was synthesized. The target β-alkyl substituted hexaphyrin (1.1.1.1.1.1) was seemed to be unstable in free base and neutral state, so reproducibility of the reaction was very low and characterization had been carried out only in the protonated form to date. This time, the synthetic method was revised and the reaction intermediate was isolated before oxidized. As aresult, the final step of the purification was dramatically simplified and reproducibility of the reaction was raised. Furthermore, the quick working up made it possible to measure ^1H NMR spectrum of the neutral state of hexaphyrin. This observation revealed that two inner meso-protons of neutral hexaphyrin was pointing inward of the macrocycle in the similar maaner to the protonated form. Moreover, zinc complex of the hexaphyrin was more stable than the free base. This complex showed strong aromaticity and optical property analogous to porphyrin. This is the first example that maintains the inherent aromaticity of the parent molecule among zinc complexes of hexaphyrins (1.1.1.1.1.1) or general metalcomplexes of meso-free hexaphyrins (1.1.1.1.1.1). Good single crystals of the zinc complex suitable for X-ray analysis were obtained, but coordination with the other metals was not achieved. On the other hand, unique bis-BF_2 and bis-Rh(CO)_2 complexes of non-conjugated macrocyclic bis-dipyrrin units were synthesized using the isolated intermediate.
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