Yu Yinghua, Shen Si-Hao, Chen Jian-Bing, Ding Qing-Rong, Zhang Hai-Xia, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, P. R. China.
University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100049, P. R. China.
J Am Chem Soc. 2025 Jun 18;147(24):20770-20777. doi: 10.1021/jacs.5c04285. Epub 2025 Jun 6.
The construction of helical polymer nanotubes with precise structure and enhanced stability remains a formidable challenge in synthetic chemistry, as it requires a complex balance of covalent and noncovalent interactions for hierarchical assembly. Herein, we report a hierarchical self-assembly strategy for the single-crystal synthesis of homochiral helical polymer nanotubes from simple, commercially available achiral monomers via synergistic dynamic covalent chemistry and noncovalent interactions. This one-pot process integrates the in situ formation of boroxine-based dynamic covalent bonds (B-O and B-N) to establish the polymer backbone, longitudinal hydrogen bonding (C≡N···H-N) to induce helical coiling, and π-π stacking to stabilize the enclosed nanotubular architecture. Through single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy, we elucidate a crystallization-induced helical (CIH) nanotubulization mechanism, wherein linear polymer chains undergo supramolecular reorganization into homochiral helices during crystallization. The resulting nanotubes exhibit intrinsic chirality, hydrophilicity, aqueous stability, and strong photoluminescence properties. This work establishes a scalable, modular platform for synthesizing crystalline helical nanomaterials, bridging the gap between covalent polymer synthesis and nanotube design engineering for advanced optoelectronic and enantioselective applications.
构建具有精确结构和更高稳定性的螺旋聚合物纳米管在合成化学中仍然是一项艰巨的挑战，因为这需要共价和非共价相互作用之间复杂的平衡以进行分级组装。在此，我们报道了一种分级自组装策略，通过协同动态共价化学和非共价相互作用，从简单的市售非手性单体单晶合成同手性螺旋聚合物纳米管。这个一锅法过程整合了基于硼酸酯的动态共价键（B-O和B-N）的原位形成以建立聚合物主链、纵向氢键（C≡N···H-N）以诱导螺旋卷曲以及π-π堆积以稳定封闭的纳米管结构。通过单晶X射线衍射和圆二色（CD）光谱，我们阐明了一种结晶诱导螺旋（CIH）纳米管形成机制，其中线性聚合物链在结晶过程中经历超分子重排形成同手性螺旋。所得纳米管具有固有手性、亲水性、在水中的稳定性以及强的光致发光特性。这项工作建立了一个用于合成结晶螺旋纳米材料的可扩展、模块化平台，弥合了共价聚合物合成与用于先进光电和对映选择性应用的纳米管设计工程之间的差距。
