SYNTHESIS OF STRAPPED, DIMERIC, AND TRIMERIC PORPHYRINS BASED ON INTRAMOLECULAR MACROCYCLIZATION REACTIONS
SYNTHESIS OF STRAPPED, DIMERIC, AND TRIMERIC PORPHYRINS BASED ON INTRAMOLECULAR MACROCYCLIZATION REACTIONS
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DOI：
10.1246/bcsj.64.1213
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发表时间：
1991-01-01
影响因子：
4
通讯作者：
MARUYAMA, K
中科院分区：
文献类型：
--
作者：
OSUKA, A;KOBAYASHI, F;MARUYAMA, K
带状卟啉是通过 3,3'-二乙基-4,4'-二甲基-2,2'-二吡基甲烷和具有长于 7 个原子的带状键的亚甲二氧基桥联二醛的酸催化缩合反应直接制备的。作为该方法的应用，具有共面和正交（T 形）几何形状的二聚体和三聚体卟啉也以良好的产率合成。在带状卟啉中，卟啉环的畸变随着带键的缩短而系统性地增加，这已被它们的 H-1 NMR 数据、红移吸收和荧光光谱所证实。在共面二聚体和三聚体卟啉中，清楚地观察到卟啉之间的电子相互作用，而在正交的“T形”二聚体和“H形”三聚体中，没有观察到明显的电子相互作用。
Strapped porphyrins were prepared directly by the acid-catalyzed condensation reaction of 3,3'-diethyl-4,4'-dimethyl-2,2'-dipyrrylmethane and methylenedioxy bridged dialdehydes having a strap linkage longer than 7 atoms. Dimeric and trimeric porphyrins with coplanar and orthogonal (T-shape) geometries were also synthesized in good yields as an application of this method. In the strapped porphyrins, the distortion of porphyrin ring increases systematically on shortening the strap linkage, which is confirmed by their H-1 NMR data, red shifted absorption, and fluorescence spectra. In the coplanar dimeric and trimeric porphyrins, the electronic interactions between the porphyrins were distinctly observed, while in the orthogonal ''T-shaped'' dimers and ''H-shaped'' trimers, appreciable electronic interactions were not observed.