Chan Chun Lam Clement, Ostermann Emily C, Maguire Shawn M, Schmidt Zachary, Votava Jacob S, Wąsik Patryk, Webb Michael A, Davidson Emily C
Department of Chemical and Biological Engineering, Princeton University, Princeton, NJ 08544, USA.
National Synchrotron Light Source II, Complex Scattering Program, Brookhaven National Laboratory, Upton, NY 11973, USA.
Sci Adv. 2025 Aug 22;11(34):eadw5327. doi: 10.1126/sciadv.adw5327. Epub 2025 Aug 20.
Understanding how different forms of supramolecular curvature arise during assembly is crucial to designing and tuning the microstructure of hierarchically self-assembled materials. Here, we show that in crystalline phases of mesogenic oligomers, the oligomer length is a critical parameter that determines the type of curvature (Gaussian or cylindrical) exhibited by the self-assembled structures. We use iterative exponential growth to synthesize monodisperse mesogenic oligomers ranging from dimer to octamer. By analyzing their phase behavior and microstructure, we elucidate how length-dependent thermodynamic and kinetic effects tune their hierarchical degree of ordering. The oligomers' length-dependent crystalline order drives the formation of scrolled sheets in shorter oligomers and twisted ribbons in longer oligomers. These studies highlight how oligomer length interplays with mesogen geometry and crystalline packing to drive self-assembly, introducing oligomer length as a powerful design parameter toward tailored applications of mesogenic systems.
了解在组装过程中如何产生不同形式的超分子曲率对于设计和调整分层自组装材料的微观结构至关重要。在这里，我们表明，在介晶低聚物的晶相中，低聚物长度是一个关键参数，它决定了自组装结构所呈现的曲率类型（高斯曲率或圆柱曲率）。我们使用迭代指数增长来合成从二聚体到八聚体的单分散介晶低聚物。通过分析它们的相行为和微观结构，我们阐明了长度依赖性的热力学和动力学效应如何调节它们的分层有序度。低聚物的长度依赖性晶体有序性驱动较短低聚物中形成卷曲片层，而在较长低聚物中形成扭曲带。这些研究突出了低聚物长度如何与介晶几何形状和晶体堆积相互作用以驱动自组装，将低聚物长度作为介晶系统定制应用的一个强大设计参数引入。
