Expanded π-electron systems, tri(phenanthro)hexaazatriphenylenes and tri(phenanthrolino)hexaazatriphenylenes, that are self-assembled to form one-dimensional aggregates.
Expanded π-electron systems, tri(phenanthro)hexaazatriphenylenes and tri(phenanthrolino)hexaazatriphenylenes, that are self-assembled to form one-dimensional aggregates.
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DOI：
10.1021/jo101212d
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发表时间：
2010-09
期刊：
影响因子：
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通讯作者：
Tsutomu Ishi‐i;Ryo Hirashima;N. Tsutsumi;Shogo Amemori;S. Matsuki;Y. Teshima;Rempei Kuwahara;S. Mataka*
中科院分区：
文献类型：
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作者：
Tsutomu Ishi‐i;Ryo Hirashima;N. Tsutsumi;Shogo Amemori;S. Matsuki;Y. Teshima;Rempei Kuwahara;S. Mataka*
本文报道了具有扩展π电子体系的六氮杂苯类缺电子杂环化合物的自组装和电化学性质。通过相应的菲醌和菲咯啉二酮分别与六氨基苯的缩合反应，合成了三菲并六氮杂三亚苯（TPHAT-Cs）和三菲并六氮杂三亚苯（TPHAT-Ns）。它们的电子亲和性由循环伏安法测量指示，其中在二氯甲烷中在约-1.7V（相对于Fc/Fc（+））下评估第一还原电位。在非极性和极性溶剂中以及薄膜状态下，TPHAT-Cs和TPHAT-Ns形成了具有H型平行堆积模式的一维聚集体。在MALDI-TOF质谱中，在母体离子的几个倍数直至四聚体聚集体处观察到显著峰。（1）H NMR谱表明由于聚集而导致的谱线增宽效应。紫外-可见光谱和荧光光谱显示出浓度依赖性，这是由于单体和聚集体物种之间的动态交换。聚集性质的顺序估计从浓度依赖性和荧光量子产率。通过用邻菲咯啉（TPHAT-Ns）代替菲（TPHAT-Cs）的外围芳族部分，增强了聚集性质。
This paper reports the self-assembling and electrochemical nature of hexaazatriphenylene-based electron-deficient heteroaromatics with an expanded π-electron system. The tri(phenanthro)hexaazatriphenylenes (TPHAT-Cs) and tri(phenanthrolino)hexaazatriphenylenes (TPHAT-Ns) were prepared by condensation reactions of the corresponding phenanthrenequinones and phenanthrolinediones, respectively, with hexaaminobenzene. Their electron affinity was indicated from cyclic voltammetry measurements, in which the first reduction potentials were evaluated at around -1.7 V (vs Fc/Fc(+)) in dichloromethane. In nonpolar and polar solvents and in the film state, the TPHAT-Cs and TPHAT-Ns formed one-dimensional aggregates with an H-type parallel stacking mode. In the MALDI-TOF mass spectra, significant peaks were seen at several multiples of the parent ion up to tetramer aggregates. The (1)H NMR spectra indicated a line-broadening effect due to the aggregation. The UV-vis and fluorescence spectra showed a concentration dependence, which is attributed to a dynamic exchange between the monomer and aggregate species. The order of the aggregative nature was estimated from the concentration dependence and the fluorescence quantum yield. By replacement of the peripheral aromatic moieties instead of the phenanthrene (TPHAT-Cs) with the phenanthroline (TPHAT-Ns), the aggregative nature was enhanced.