Coiled-coil gel nanostructures of oligo(p-phenylenevinylene)s:: Gelation-induced helix transition in a higher-order supramolecular self assembly of a rigid π-conjugated system
Coiled-coil gel nanostructures of oligo(p-phenylenevinylene)s:: Gelation-induced helix transition in a higher-order supramolecular self assembly of a rigid π-conjugated system
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DOI：
10.1002/anie.200453874
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Meijer, EW
中科院分区：
文献类型：
--
作者：
George, SJ;Ajayaghosh, A;Meijer, EW
生物分子超分子组装成螺旋纳米结构的有趣现象，如脱氧核糖核酸双螺旋、胶原三螺旋和肌球蛋白的α卷曲，一直吸引着科学家。在氢键、π堆积和范德华相互作用等非共价力的帮助下，化学家们已经能够设计出各种美观的螺旋超分子组件。[1，2]在这种情况下，将π共轭体系的超分子组织控制成纳米维度的螺旋是至关重要的，因为所得到的结构可以应用于新兴的超分子电子学领域，因为它们具有独特的光学和电子性质。[3]有机分子自发自组装形成凝胶是一种创建纳米和介观结构的方法。手性分子的凝胶化形成螺旋结构已经引起了人们的极大关注。[5-8]最近，通过偶然的观察，我们展示了官能化低聚对苯乙叉S(OPV)的凝胶化及其在光捕获中的应用。[9]在这里，我们报道了一个有趣的例子，在刚性π共轭体系的分级自组装过程中，凝胶辅助的螺旋转变形成了卷曲螺旋绳索。在这种情况下，凝胶诱导的螺旋形成是由一对遥远的手性手柄促进的，并由弱的氢键基序和长碳氢链辅助，从而使分子有足够的自由进行自组装。
The intriguing phenomenon of the supramolecular assembly of biological molecules into helical nanostructures, such as the DNA double helix, the collagen triple helix, and the α coiledcoil of myosin, has always fascinated scientists. With the help of noncovalent forces, such as hydrogen bonding, π stacking, and van der Waals interactions, chemists have been able to design a variety of aesthetically appealing helical supramolecular assemblies.[1, 2] In this context, the control of the supramolecular organization of π-conjugated systems into helices of nanoscopic dimensions is of the utmost importance, as the resulting structures could find application in the emerging area of supramolecular electronics because of their unique optical and electronic properties.[3] The spontaneous self-assembly of organic molecules to form gels is a method for creating nanoscopic and mesoscopic structures.[4] In particular, the gelation of chiral molecules to form helical morphologies has received considerable attention.[5–8] Recently, through a serendipitous observation, we showed the gelation of functionalized oligo (p-phenylenevinylene) s (OPVs) and their application in light harvesting.[9] Herein we report an interesting case of a gelation-assisted helix transition during the hierarchical self-assembly of a rigid π-conjugated system to form coiled-coil helical ropes. The gelation-induced helix formation in the present case is promoted by a pair of remote chiral handles and assisted by weak hydrogen-bonding motifs and long hydrocarbon chains, thus allowing the molecules sufficient freedom to undergo self-assembly.