Preparation and Characterization of N-Anisyl-Substituted Hexaaza[16]paracyclophane
Preparation and Characterization of N-Anisyl-Substituted Hexaaza[16]paracyclophane
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DOI：
10.1002/anie.201002165
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Tanaka, Kazuyoshi
中科院分区：
文献类型：
--
作者：
Ito, Akihiro;Yokoyama, Yuichiro;Tanaka, Kazuyoshi
与碳桥杯芳烃不同的是，杂原子桥[1]间环芳烷及其衍生物近年来引起了人们的广泛关注，这主要是由于杂原子桥取代亚甲基桥所带来的新颖的结构-性能关系。[2]另一方面，只有少数报道是已知的[1 n] paracyclophanes，可能是由于在合成它们的困难（方案1）。[3，4]氮杂[1 n]对环芳类化合物是聚苯胺的大环低聚物，聚苯胺是一种有机导电高分子。[5]从简单的Hückel MO计算可以明显看出，线性和环状低聚苯胺的HOMO呈现不同的方面，如方案2所示。对于线性六聚体，大的MO系数集中在中心对苯二胺（PD）部分。由于线性苯胺齐聚物的HOMO定域性，其自由基阳离子的ESR研究表明，自旋仅限于中心PD部分，
As opposed to the thoroughly studied carbon-bridged calixarenes,[1] heteroatom-bridged [1n] metacyclophanes and their derivatives have recently attracted much attention mainly because of novel structure-property relationships originating from the replacement of methylene bridges with heteroatom bridges.[2] On the other hand, only a few reports are known for [1n] paracyclophanes, probably as a result of the difficulty in synthesizing them (Scheme 1).[3, 4]Aza [1n] paracyclophanes can be viewed as macrocyclic oligomers of polyaniline, which is one of the well-known organic conducting polymers.[5] As is apparent from the simple Hückel MO calculations, the HOMOs for linear and cyclic oligoanilines assume different aspects, as exemplified in Scheme 2. As for the linear hexamer, the large MO coefficients are concentrated on the central para-phenylenediamine (PD) moiety. Owing to the localized HOMO character, the ESR studies on the radical cations of linear oligoanilines showed that the spin was confined to the central PD moiety,