A Successful Chemical Strategy To Induce Oligothiophene Self-Assembly into Fibers with Tunable Shape and Function
A Successful Chemical Strategy To Induce Oligothiophene Self-Assembly into Fibers with Tunable Shape and Function
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DOI：
10.1021/ja2014949
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发表时间：
2011-06-08
影响因子：
15
通讯作者：
Barbarella, Giovanna
中科院分区：
文献类型：
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作者：
Di Maria, Francesca;Olivelli, Pasquale;Barbarella, Giovanna
自下而上的有机纳米和微米技术的功能超分子结构是一个高度优先的研究课题。我们发现了一种新的识别算法，导致从硫代烷基取代基和头对头的区域化学取代的组合，诱导自发自组装的硫过丰富的octathiophenes到超分子晶体纤维结合高电荷迁移率和强烈的荧光。纤维生长在各种类型的表面上，根据分子结构，可以是超螺旋或直杆。直接生长在场效应晶体管上的螺旋纤维显示出高效的电荷迁移率和固有的“记忆效应”。尽管事实上，低聚物没有手性中心，一种类型的手螺旋总是占主导地位的螺旋纤维，由于分子阻转异构和超分子螺旋诱导的末端取代基的相互作用。最后，我们发现在绿色条件下，通过超声波和微波辅助可以容易地以高产率制备新的过富硫低聚噻吩。
Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and sup ramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.