An Adjacent Dibenzotetraazaporphyrin: A Structural Intermediate between Tetraazaporphyrin and Phthalocyanine.
An Adjacent Dibenzotetraazaporphyrin: A Structural Intermediate between Tetraazaporphyrin and Phthalocyanine.
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相邻的二苯并四氮杂卟啉：四氮杂卟啉和酞菁之间的结构中间体。
DOI：
10.1021/ic9806535
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发表时间：
1999
影响因子：
4.6
通讯作者：
T. Tomura
中科院分区：
文献类型：
--
作者：
N. Kobayashi;Hideya Miwa;Hiroaki Isago;T. Tomura
首次合成了一个相邻的二苯并四氮杂卟啉铜配合物，其中两个苯单元与四氮杂卟啉骨架上相邻的吡咯环稠合，并通过电子吸收光谱、磁圆二色谱、循环伏安和光谱电化学等方法进行了表征.与四氮杂卟啉和酞菁类似物的结果进行了比较。标题化合物显示正常的四氮杂卟啉和酞菁之间的中间特征; Q-带移动到红色，变得更加强烈，而Soret带加宽与π系统的大小增加。随着π系统的膨胀，第一还原电位没有显著变化，而第一氧化电位负移，表明LUMO能级几乎保持恒定，而HOMO能级显著不稳定。这些光谱性质和氧化还原电位再现分子轨道计算的框架内的Pariser-Parr-Pople近似。热重分析表明，相邻的二苯并四氮杂卟啉配合物的骨架分解在约95度低于四叔丁基酞菁类似物。
An adjacent dibenzotetraazaporphyrin, in which two benzene units are fused to the adjacent pyrrole rings of tetraazaporphyrin skeleton, has been synthesized as a copper complex for the first time and characterized by electronic absorption and magnetic circular dichroism spectroscopy, by cyclic voltammetry and spectroelectrochemistry using an optically transparent thin layer electrochemical cell. The results were compared with those of tetraazaporphyrin and phthalocyanine analogues. The title compound shows intermediate characteristics between those of normal tetraazaporphyrins and phthalocyanines; the Q-band shifts to the red and becomes more intense while the Soret band broadens with increasing the size of the pi-system. With the expansion of the pi-system, the first reduction potential does not change significantly, while the first oxidation potential shifts negatively, indicating that the LUMO level remains almost constant while the HOMO level destabilizes significantly. These spectroscopic properties and redox potentials were reproduced by molecular orbital calculations within the framework of the Pariser-Parr-Pople approximation. Thermogravimetry analysis suggests that the skeleton of the adjacent dibenzotetraazaporphyrin complex decomposes at about 95 degrees lower than that of the tetra-tert-butylated phthalocyanine analogue.