Development of Porphyrinoid Materials Aimed at Non-linear Optics and Photodynamic Therapy

旨在开发非线性光学材料或光动力疗法药物的新型卟啉类化合物的合成已经开始。首先，由于在按照报道的方法合成低聚吡咯前体的过程中发现了不可预测的合成问题，因此对反应条件进行了修改，以抑制副产物的形成。此外，还合成了一种迄今难以引入的含吡啶环的稀有低聚吡咯单元。目标化合物β-烷基取代己酮(1.1.1.1.1.1)在游离碱和中性状态下似乎不稳定，因此反应的重现性很低，到目前为止仅以质子化形式进行表征。这一次，对合成方法进行了修改，并在氧化前分离了反应中间体。从而大大简化了纯化的最后一步，提高了反应的重现性。此外，这一快速的工作使测定己酮酸中性状态的~1H核磁共振谱成为可能。这一观察表明，在类似于质子化形式的Maner中，中性六氢呋喃的两个中间质子指向大循环的内侧。此外，六氢呋喃的锌络合物比游离碱更稳定。该配合物具有很强的芳香性和类似于卟啉的光学性质。这是第一个在六氢呋喃锌络合物(1.1.1.1.1.1)或一般金属络合物(1.1.1.1.1.1)中保持母体分子固有芳香性的例子。得到了适合于X射线分析的锌配合物的良好单晶，但与其他金属没有配位。另一方面，利用分离的中间体合成了独特的非共轭大环双二吡咯单元的双BF_2和双-Rh(CO)_2配合物。

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.