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

用于非线性光学和光动力治疗的类卟啉材料的开发

基本信息

批准号：
20850004
负责人：
SUZUKI Masaaki
金额：
$ 2.1万
依托单位：
Chiba University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Young Scientists (Start-up)
财政年份：
2008
资助国家：
日本
起止时间：
2008 至 2009
项目状态：
已结题

项目摘要

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.

以非线性光学材料或光动力治疗药物的开发为目的的新型卟啉类化合物的合成已经开始。首先，由于在根据所报道的方法合成低聚吡咯前体期间发现了不可预测的合成问题，因此修改了反应条件，从而抑制了副产物的形成。此外，还合成了一种迄今为止难以引入的带有吡啶环的罕见的低聚吡咯单元。目标产物β-烷基取代的己卟啉（1.1.1.1.1.1）在游离碱和中性状态下似乎不稳定，因此反应的重现性非常低，迄今为止仅以质子化形式进行表征。本文对合成方法进行了改进，并对反应中间体进行了分离和氧化。实验结果表明，纯化的最后一步大大简化，反应的重现性提高。此外，快速后处理使得测量中性状态的己卟啉的^1H NMR谱成为可能。这一观察结果表明，中性六卟啉的两个内部中质子以与质子化形式类似的方式指向大环的内部。此外，锌络合物的六卟啉比游离碱更稳定。该配合物具有较强的芳香性和类似卟啉的光学性质。这是在六卟啉的锌络合物（1.1.1.1.1.1）或内消旋游离六卟啉的一般金属络合物（1.1.1.1.1.1）中保持母体分子的固有芳香性的第一个实例。获得了适合于X射线分析的锌配合物的良好单晶，但未实现与其它金属的配位。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bis-BF_2和bis-Rh（CO）_2配合物。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Application of the Perimeter Model to the Assignment of the Electronic Absorption Spectra of Gold(III)Hexaphyrins with[4n+2]and[4n]π-Electron Systems

周长模型在[4n+2]和[4n]π-电子体系金(III)六菲林电子吸收光谱归属中的应用

DOI：
发表时间：
2009
期刊：
Chemistry-A European Journal 15
影响因子：
0
作者：
A.Muranaka;O.Matsushita;K.Yoshida;S.Mori;M.Suzuki;T.Furuyama;M.Uchiyama;A.Osuka;N.Kobayashi
通讯作者：
N.Kobayashi

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