Phthalocyanines of a novel structure : dinaphthotetraazaporphyrins with D2h symmetry
Phthalocyanines of a novel structure : dinaphthotetraazaporphyrins with D2h symmetry
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新型结构的酞菁：具有 D2h 对称性的二萘四氮杂卟啉
DOI：
10.1021/ic00087a003
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发表时间：
1994
影响因子：
4.6
通讯作者：
H. Konami
中科院分区：
文献类型：
--
作者：
N. Kobayashi;Tohru Ashida;T. Osa;H. Konami
酞菁（Pc）是其中苯环与四氮杂卟啉（TAP）的四个吡咯环中的每一个稠合的化合物。除了作为染料和静电复印的传统用途外，它们现在在许多领域的重要性迅速增加，如电池，光动力癌症治疗，化学传感器，分子金属和液晶。合成了两个具有D[sub 2 h]对称性的萘分子稠合四氮杂卟啉（TAPs），并报道了它们的光谱和电化学性质。这些化合物是酞菁（Pcs）的结构异构体，在这个意义上，四个苯单元稠合到TAP骨架上。与具有D[sub 4 h]对称性的MPcs（M =金属）相反，由于分子对称性的降低，Q[sub o-o]和Soret带都分裂成两个。磁性圆二色性（MCD）显示法拉第B项对应于电子吸收光谱的峰和肩，表明不包括简并态。锌配合物的荧光量子产率远小于具有D[sub 4 h]对称性的ZnPc。这些复合物的电子吸收和电化学氧化还原数据再现分子轨道（MO）计算的框架内的Pariser-Parr-Pople（PPP）近似。结果表明，该方法的效果优于PCs和单萘-TAP。«少
Phthalocyanines (Pcs) are compounds in which a benzene ring is fused to each of the four pyrrole rings of tetraazaporphyrins (TAPs). In addition to traditional uses as dyes and in xerography, they are now rapidly increasing in importance in many fields such as batteries, photodynamic cancer therapy, chemical sensors, molecular metals, and liquid crystals. Two naphthalene molecule-fused tetraazaporphyrins (TAPs) with D[sub 2h] symmetry have been synthesized, and some of their spectroscopic and electrochemical properties are reported. These compounds are structural isomers of phthalocyanines (Pcs) in the sense that four benzene units are fused to the TAP skeleton. In contrast to MPcs (M = metal) with D[sub 4h] symmetry, both the Q[sub o-o] and Soret bands split into two as a result of the lowering of the molecular symmetry. Magnetic circular dichroism (MCD) shows Faraday B terms corresponding to the peaks and shoulders of the electronic absorption spectra, indicating that no degenerate state is included. The fluorescence quantum yield of the zinc complex is much smaller than in ZnPc with D[sub 4h] symmetry. The electronic absorption and electrochemical redox data of these complexes are reproduced by molecular orbital (MO) calculations within the framework of the Pariser-Parr-Pople (PPP) approximation. The results aremore » compared with those of Pcs and mononaphtho-TAPs.« less