Liu Zhongguo, Wang Shuai, Yang Ze, Dong Xue-Hui
South China Advanced Institute of Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology, Guangzhou, 510640, China.
Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou, 510640, China.
Macromol Rapid Commun. 2023 Jan;44(1):e2200509. doi: 10.1002/marc.202200509. Epub 2022 Aug 27.
In this study, polyhedral oligomeric silsesquioxane (POSS) based giant triblock molecules with precisely defined regio-configuration are modularly prepared through highly efficient coupling reactions. The length of the linker connecting neighboring nanoparticles is elaborately designed to regulate the geometric constraints. The triblock molecules adopt a folded packing during phase separation, and the regio-configuration imparts direct influence on the self-assembly behaviors. The ortho-isomers form periodic structures with a larger domain size, larger interfacial curvature, and enhanced phase stability. The regio-effect is closely related to the length and symmetry of the linker. As the linker extends, the neighboring particles gradually decouple, and the regio-effect diminishes. The symmetry of the linker shows an even more profound impact. This work quantitatively scrutinized the role of the linker, opening an avenue for engineering the assembled structures with molecular precision.
在本研究中，通过高效偶联反应模块化制备了具有精确区域构型的基于多面体低聚倍半硅氧烷（POSS）的巨型三嵌段分子。精心设计连接相邻纳米颗粒的连接链长度以调节几何约束。三嵌段分子在相分离过程中采用折叠堆积，区域构型对自组装行为有直接影响。邻位异构体形成具有更大畴尺寸、更大界面曲率和增强相稳定性的周期性结构。区域效应与连接链的长度和对称性密切相关。随着连接链延长，相邻颗粒逐渐解耦，区域效应减弱。连接链的对称性显示出更深刻的影响。这项工作定量地审视了连接链的作用，为以分子精度设计组装结构开辟了一条途径。
