Department of Materials Science and Engineering, University of Sheffield, Sheffield, S1 3JD, UK.
Department of Physics, Zhejiang Sci-Tech University, Hangzhou, 310018, P.R. China.
Chemistry. 2019 Oct 28;25(60):13739-13747. doi: 10.1002/chem.201902639. Epub 2019 Sep 13.
Wedge-shaped molecules, such as dendrons, are among the most important building blocks for directed supramolecular self-assembly. Here we present a new approach aimed at widening the range and complexity of potential mesophases by introducing double-tapered mesogens. Two series of compounds are presented, both alkali metal salts (Li, Na, Cs) of 3,4,5-tris-alkoxybenzoic acid with a second tapered tris-alkoxyaryl group attached at the end of an alkoxy chain. The double-tapered compounds all display an unusual hexagonal columnar phase consisting of one ionic and three non-ionic columns per unit cell. The cation size has an unexpectedly drastic effect on unit cell size. Unlike most columnar phases, the current phases show unusually high dimensional stability on heating, and high stiffness in spite of being 80-85 % aliphatic, attributed to their molecular topology. The described approach may lead to co-assemblies of multifunctional materials, for example, parallel p- and n-semiconducting nanowires or parallel ionic and electronic conductors.
楔形分子,如树枝状大分子,是用于定向超分子自组装的最重要的结构单元之一。在这里,我们提出了一种新方法,旨在通过引入双锥形介晶来拓宽潜在介相的范围和复杂性。我们提出了两个系列的化合物,它们都是 3,4,5-三烷氧基苯甲酸的碱金属盐(Li、Na、Cs),在烷氧基链的末端连接了第二个锥形三烷氧基芳基基团。所有的双锥形化合物都显示出一种不寻常的六方柱状相,每个单元晶胞由一个离子和三个非离子柱组成。阳离子的大小对单元晶胞的大小有出乎意料的剧烈影响。与大多数柱状相不同,目前的相在加热时表现出异常高的尺寸稳定性和高刚性,尽管它们有 80-85%是脂肪族的,这归因于它们的分子拓扑结构。所描述的方法可能会导致多功能材料的共组装,例如,平行的 p 和 n 型半导体纳米线或平行的离子和电子导体。