Combination of an aromatic core and aromatic side chains which constitutes discotic liquid crystal and organogel supramolecular assemblies.
Combination of an aromatic core and aromatic side chains which constitutes discotic liquid crystal and organogel supramolecular assemblies.
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DOI：
10.1021/la047874
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发表时间：
2005-01
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影响因子：
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通讯作者：
Tsutomu Ishi‐i;Tomoyuki Hirayama;Kohshi Murakami;H. Tashiro;T. Thiemann;K. Kubo;A. Mori;S. Yamasaki;T. Akao;A. Tsuboyama;T. Mukaide;K. Ueno;S. Mataka*
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文献类型：
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作者：
Tsutomu Ishi‐i;Tomoyuki Hirayama;Kohshi Murakami;H. Tashiro;T. Thiemann;K. Kubo;A. Mori;S. Yamasaki;T. Akao;A. Tsuboyama;T. Mukaide;K. Ueno;S. Mataka*
本文报道了由芳香族六氮杂苯（HAT）核和六条柔性芳侧链组成的盘状分子自组装形成的独特的柱状液晶和有机凝胶。在HAT衍生物3a（4′-（N，N-二苯基）联苯-4-基链）、3b（4′-[N-（2-萘基）-N-苯基]联苯-4-基链）和3c（4′-苯氧联苯-4-基链）中，它们在液晶相中通过自组装形成二维六边形填料，并用偏光显微镜、差示扫描量热法和x射线衍射分析对其进行了表征。在某些溶剂中，HAT分子3a-c可形成粘弹性流体有机凝胶，由HAT分子组成的一维聚集体自组装并纠缠成三维网络结构。通过扫描电镜观察、(1)核磁共振、紫外-可见光谱和圆二色光谱分析了有机凝胶的结构。与3a-c相比，含有短芳侧链的3d和3e（含苯基间隔）和不含末端二芳胺和苯氧基的3f（除少数特定溶液外）和3g均不能形成液晶相和有机凝胶相。在3a-c中，带有末端柔性基团的芳香侧链与六叠氮苯基核心的硬区共同构成了稳定液晶和有机凝胶超分子结构的软区。
This paper reports unique and unusual formations of columnar liquid crystals and organogels by self-assembling discotic molecules, which are composed of an aromatic hexaazatriphenylene (HAT) core and six flexible aromatic side chains. In HAT derivatives 3a, with 4'-(N,N-diphenylamino)biphenyl-4-yl chains, 3b, with 4'-[N-(2-naphthyl)-N-phenylamino]biphenyl-4-yl chains, and 3c, with 4'-phenoxybiphenyl-4-yl chains, the two-dimensional hexagonal packings can be created by their self-assembling in the liquid crystalline phase, which were characterized by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction analysis. In certain solvents, HAT molecules 3a-c can form the viscoelastic fluid organogels, in which one-dimensional aggregates composed of the HAT molecules are self-assembled and entangled into three-dimensional network structures. The organogel structures were analyzed by scanning electron microscopy observation, (1)H NMR, UV-vis, and circular dichroism spectroscopy. In contrast to 3a-c, none of the liquid crystalline and organogel phases could be formed from 3d and 3e with short aromatic side chains including a phenylene spacer, and 3f (except a few specific solutions) and 3g without terminal diarylamino and phenoxy groups. In 3a-c, the aromatic side chains with terminal flexible groups make up soft regions that cooperatively stabilize the liquid crystalline and organogel supramolecular structures together with the hard regions of the hexaazatriphenylene core.