Crowding-Induced Unconventional Phase Behaviors in Dendritic Rodlike Molecules via Side-Chain Engineering,ACS Macro Letters

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Crowding-Induced Unconventional Phase Behaviors in Dendritic Rodlike Molecules via Side-Chain Engineering
ACS Macro Letters ( IF 5.1 ) Pub Date : 2021-06-23 , DOI: 10.1021/acsmacrolett.1c00080
Xiaobo Liu ₁ , Ruimeng Zhang _{1,

2} , Yu Shao ₃ , Liguo Xu _{1,

4} , Guorui He ₁ , Jiahao Huang _{1,

2} , Zi-Hao Guo _{1,

4} , Wen-Bin Zhang ₃ , Wen Tang _{1,

4} , Kan Yue _{1,

4}

Affiliation

Dendritic molecules with a fanlike or conelike conformation are common molecular building blocks to construct supramolecular columnar or spherical phases. Although it is well-accepted that the preferred molecular conformation of dendritic molecules dictates their packing schemes, manipulation of this crucial parameter usually requires significant changes in molecular structures and tedious synthetic efforts. Herein, we report a simple yet highly efficient strategy to tune the molecular conformation of dendritic rodlike molecules by adjusting the length of alkyl side chains tethered to the rods. Strikingly, tiny chemical structure differences can largely change the “crowding” near the branching point to induce the “fanlike to conelike” conformational transitions and thus result in the formation of diverse supramolecular structures, including the columnar phase, double gyroid phase, and the unconventional Frank–Kasper σ and A15 phases. Our study provides a practical platform for further investigation of unconventional structure formation and phase transitions in soft matter.

中文翻译：

通过侧链工程在树枝状棒状分子中拥挤诱导的非常规相行为

具有扇状或锥状构象的树枝状分子是构建超分子柱状或球形相的常见分子构件。尽管人们普遍认为树枝状分子的首选分子构象决定了它们的包装方案，但操纵这一关键参数通常需要对分子结构进行重大改变和繁琐的合成工作。在这里，我们报告了一种简单而高效的策略，通过调整拴在棒上的烷基侧链的长度来调整树枝状棒状分子的分子构象。引人注目的是，微小的化学结构差异可以在很大程度上改变分支点附近的“拥挤”，从而诱导“扇形到锥形”的构象转变，从而导致形成不同的超分子结构，包括柱状相、双螺旋相和非常规的 Frank-Kasper σ 相和 A15 相。我们的研究为进一步研究软物质中非常规结构的形成和相变提供了一个实用的平台。

更新日期：2021-07-20

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