Crystal Structures and Electronic Properties of Saddle-Distorted and Protonated Phthalocyanines
Crystal Structures and Electronic Properties of Saddle-Distorted and Protonated Phthalocyanines
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DOI：
10.1002/anie.201006607
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发表时间：
2011-01-01
影响因子：
16.6
通讯作者：
Fukuzumi, Shunichi
中科院分区：
文献类型：
--
作者：
Honda, Tatsuhiko;Kojima, Takahiko;Fukuzumi, Shunichi
酞菁（Phthalocyanines，Pcs）是一类与卟啉类化合物一起被开发的杂大环化合物，特别是作为染料和颜料。最近，它们已被用于各种应用，如光敏剂、光伏材料等。[1，2]然而，由于与卟啉环相比，酞菁环的刚性结构产生的质子化物质的碱性低，因此对由酸碱反应产生的质子化物质的性质知之甚少。[3，4]与总是发生在吡咯氮原子上的卟啉环的质子化形成鲜明对比，[5，6]酞菁可以在两个不同的位置进行质子化：异吲哚氮原子和介氮原子。到目前为止，酞菁的质子化已被限制在过酸性条件下，如在浓硫酸和三氟乙酸（TFA），因为质子化物质的小的形成常数。[3]此外，还没有任何报告，无论是在异吲哚氮原子的内部质子化的检测或质子化的酞菁的晶体结构determinations.We以前研究的鞍形扭曲的十二苯基卟啉（H2DPP），它具有来自吡咯氮原子的孤对高碱性质子化的基础上形成的超分子组装。[6]我们还报道了化合物的游离碱和金属络合物。
Phthalocyanines (Pcs) are one of the most developed heteromacrocycles, together with porphyrins, in particular as dyes and pigments. Recently, they have been utilized in a variety of applications such as photosensitizers, photovoltaic materials, and so on.[1, 2] However, the properties of protonated species resulting from the acid–base reaction have been little known because of their low basicity arising from the rigid structure of the phthalocyanine ring as compared with the porphyrin ring.[3, 4] In sharp contrast to the protonation of the porphyrin ring, which always occurs at pyrrole nitrogen atoms,[5, 6] phthalocyanines may undergo protonation at two different sites: the isoindole nitrogen atom and the mesonitrogen atom. To date, the protonation of phthalocyanines has been limited to overly acidic conditions such as in concentrated sulfuric acid and in trifluoroacetic acid (TFA) because of the small formation constants of protonated species.[3] Moreover, there have been no reports on either the detection of inner protonation at the isoindole nitrogen atom or of the crystal structure determination of protonated phthalocyanines.We previously investigated the formation of supramolecular assemblies based on the protonation of saddle-distorted dodecaphenylporphyrin (H2DPP), which has high basicity derived from the lone pairs of pyrrole nitrogen atoms.[6] We have also reported on the free base and the metal complex of