Kudoh Yuta, Suzuki Emi, Ochiai Hikari, Ise Kakeru, Kimura Yoshifumi, Minoura Mao, Nakano Haruyuki, Matano Yoshihiro
Department of Fundamental Sciences, Graduate School of Science and Technology, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Department of Applied Chemistry, Graduate School of Science and Engineering, Doshisha University, Kyotanabe, 610-0321, Japan.
Chemistry. 2023 Nov 2;29(61):e202302148. doi: 10.1002/chem.202302148. Epub 2023 Sep 28.
The fundamental properties of azaporphyrins can be modulated over a wide range by changing the number of meso-nitrogen atoms. Reported herein are the first examples of 5,10,15,20-tetraaryl-5-azaporphyrinium (MTAMAP) salts, which were prepared via metal-templated cyclization of the corresponding zinc(II) and copper(II) complexes of 10-aryl-1-chloro-19-benzoyl-5,15-dimesityl-10-azabiladiene-ac. The inclusion of one meso-nitrogen atom in the 5,10,15,20-tetraarylporphyrin skeleton considerably changes the redox and optical properties as well as the degree of aromaticity of the porphyrin ring. The present findings suggest that MTAMAP salts would be promising scaffolds for the development of new azaporphyrin-based ionic fluorophores and photosensitizers.
通过改变中位氮原子的数量，可以在很宽的范围内调节氮杂卟啉的基本性质。本文报道了5,10,15,20-四芳基-5-氮杂卟啉鎓（MTAMAP）盐的首个实例，其通过10-芳基-1-氯-19-苯甲酰基-5,15-二甲基苯基-10-氮杂二烯酸的相应锌（II）和铜（II）配合物的金属模板环化反应制备而成。在5,10,15,20-四芳基卟啉骨架中引入一个中位氮原子会显著改变卟啉环的氧化还原和光学性质以及芳香性程度。目前的研究结果表明，MTAMAP盐有望成为开发新型氮杂卟啉基离子荧光团和光敏剂的支架。
