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Supramolecular Self-Assembly of Perylene Bisimide-Based Rigid Giant Tetrahedra.
ACS Nano ( IF 15.8 ) Pub Date : 2020-06-24 , DOI: 10.1021/acsnano.0c01971
Jiahao Huang 1, 2 , He Ren 2, 3 , Rongchun Zhang 1 , Lidong Wu 4 , Yuanming Zhai 5 , Qingyi Meng 4 , Jing Wang 1 , Zebin Su 2 , Ruimeng Zhang 2 , Shuqi Dai 1 , Stephen Z D Cheng 1, 2 , Mingjun Huang 1
Affiliation  

Recently, ordered structures constructed from rigid three-dimensional (3D) shaped polyhedra have been drawing general interest, with the tetrahedron being the simplest one but showing complicated assembly behaviors. Rigid tetrahedron building blocks have been shown to form quasicrystalline and crystalline phases with high packing fractions by both simulation and experiments. Nevertheless, the study of 3D tetrahedral building blocks is limited, especially in the field of supramolecular self-assembly. Here, we present an experimental study of rigid giant tetrahedral molecules constructed by attaching four bulky polyhedral oligomeric silsesquioxane (POSS) cages to a tetrahedral perylene bisimide (PBI) scaffold. Self-assembly of these giant tetrahedra is mediated by π–π interaction between the tetrahedral PBI-based scaffolds and their overall tetrahedral symmetry. A monolithic nearly centimeter-sized hexagonal supramolecular structure was observed in the giant tetrahedron with short flexible linkers between PBI and POSS cages, while a micrometer-sized crystalline helical structure formed in that with completely rigid aromatic linkers. Their significant difference in electrical conductivity could be explained by two completely different packing models of the giant tetrahedra.

中文翻译:

基于Per双酰亚胺的刚性巨型四面体的超分子自组装。

最近,由刚性三维(3D)形状的多面体构造的有序结构引起了人们的普遍兴趣,其中四面体是最简单的结构,但显示出复杂的组装行为。刚性四面体构件已通过模拟和实验显示形成高填充分数的准晶相和晶相。尽管如此,对3D四面体构造块的研究仍然有限,尤其是在超分子自组装领域。在这里,我们介绍了通过将四个庞大的多面体低聚倍半硅氧烷(POSS)笼连接到四面体bi双酰亚胺(PBI)支架上而构建的刚性巨型四面体分子的实验研究。这些巨大的四面体的自组装由四面体基于PBI的支架之间的π-π相互作用及其整体四面体对称性介导。在巨大的四面体中观察到一个整体的近厘米大小的六边形超分子结构,在PBI和POSS笼之间具有短的柔性连接子,而在其中形成的微米大小的晶体螺旋结构具有完全刚性的芳族连接子。它们在电导率上的显着差异可以用巨型四面体的两种完全不同的堆积模型来解释。而微米级的晶体螺旋结构则以完全刚性的芳族连接基形成。它们在电导率上的显着差异可以用巨型四面体的两种完全不同的堆积模型来解释。而微米级的晶体螺旋结构则以完全刚性的芳族连接基形成。它们在电导率上的显着差异可以用巨型四面体的两种完全不同的堆积模型来解释。
更新日期:2020-07-28
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