Jiang Xin, Xu Yaping, Zhang Haixin, Yu Hao, Han Ningxu, Guo Xu, Gao Zinuo, Zhang Xinrui, Li Haopeng, Ge Lei, Han Jiaqi, Shen Shaocheng, Yu Jing, Wang Kun, Qiu Yunyan, Wang Ming
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun 130012 China.
Department of Chemistry, National University of Singapore 117543 Singapore.
Chem Sci. 2025 Aug 28. doi: 10.1039/d5sc03463a.
Despite advances in non-covalent interactions and complex self-assembly, precise control of multi-dimensional hierarchical self-assembly (HSA) from the molecular level to larger scales remains challenging. Herein, we designed and synthesized two rigid tetratopic ligands with multiple preset driving forces, and assembled them with Zn(ii) ions to obtain metallacages SC6 and SC12. Through balancing multiple non-covalent interactions, including metal-organic coordination, hydrophobic, and π-π interactions, SC6 can hierarchically self-assemble driven by a poor solvent, from one-dimensional nanowires to super-helical nanostructures non-equilibrium self-assembly, progressing continuously with time and the increasing proportion of the poor solvent. However, for SC12 with enhanced hydrophobic interactions, two-dimensional monolayer nanogrids were formed by hierarchical self-assembly. Notably, these structures can be recycled back to primary metallacages through simple dissolution, highlighting their potential for efficient recycling and reuse. These results demonstrate that multi-dimensional hierarchical structures enable precise construction by balancing non-covalent interactions through a bottom-up self-assembly approach. This study provides deeper insight into the mechanisms of HSA and a promising strategy for the tailored creation of complex structures and sustainable porous materials.
尽管在非共价相互作用和复杂的自组装方面取得了进展，但从分子水平到更大尺度精确控制多维分级自组装（HSA）仍然具有挑战性。在此，我们设计并合成了两种具有多种预设驱动力的刚性四齿配体，并将它们与锌（II）离子组装，得到金属笼SC6和SC12。通过平衡多种非共价相互作用，包括金属-有机配位、疏水和π-π相互作用，SC6可以在不良溶剂的驱动下分级自组装，从一维纳米线到超螺旋纳米结构——非平衡自组装，随着时间和不良溶剂比例的增加而持续进行。然而，对于具有增强疏水相互作用的SC12，通过分级自组装形成了二维单层纳米网格。值得注意的是，这些结构可以通过简单溶解回收为初级金属笼，突出了它们高效回收和再利用的潜力。这些结果表明，多维分级结构能够通过自下而上的自组装方法平衡非共价相互作用来精确构建。这项研究为HSA的机制提供了更深入的见解，并为定制复杂结构和可持续多孔材料提供了一种有前景的策略。
