近日，苏州大学仲启刚团队研究了基于层次超分子自组装的等规双链环烯聚合物的表面合成。2026年2月9日，《美国化学会志》发表了这一成果。

表面合成技术已彻底革新功能纳米结构的构筑方法。然而迄今为止，在这一研究范畴内，聚合物立构规整度的概念尚未得到探索。立构规整度直接影响聚合物性质，进而决定其应用场景。例如，全同立构聚合物中取代基的全顺式排列可能形成高结晶度、高强度的材料。为此，领域内已发展出涉及手性催化剂或配体的专门方法来调控聚合物立构规整度。

研究组证明，通过将表面聚合的二维空间限域效应与单体的预组织策略相结合，可在无手性助剂条件下合成全同立构聚合物链。为验证这一理念，研究组设计合成了具有C–H···π键作用、芳香堆积及范德华相互作用能力的碗烯取代三联苯单体。这些弱相互作用引导单体在银(111)表面自组装形成有序双链结构，且碗烯取代基均定向排列于单侧。随后对自组装单体进行乌尔曼偶联聚合，成功构筑了双链全同立构聚苯撑聚合物。其立体规整性进一步促使该双链结构组装形成高阶有序结晶畴。最终，通过扫描隧道显微镜针尖的机械操控，可实现该合成聚合物双链的“解拉链”式分离，得到单个全同立构聚合物链。

附：英文原文

Title: On-Surface Synthesis of Isotactic Double-Stranded Corannulene Polymers Steered by Hierarchical Supramolecular Self-Assembly

Author: Haolin Dong, Zhongbo Zhang, Zhifang Wang, Yan Guo, Xinxin Huang, Qiang Huang, Jonas Bjrk, Johanna Rosen, Mihaiela C. Stuparu, Kaifeng Niu, Lifeng Chi, Qigang Zhong

Issue&Volume: February 9, 2026

Abstract: On-surface synthesis has revolutionized the construction of functional nanostructures. Thus far, however, the concept of polymer tacticity has remained unexplored in this context. Tacticity impacts polymer properties, which in turn governs polymer applications. An all-syn arrangement of substituents in isotactic polymers, for instance, may lead to highly crystalline, high-strength materials. Thus, specialized methods have been developed involving chiral catalysts or ligands to control polymer tacticity. In this work, we demonstrate that two-dimensional surface confinement of on-surface polymerization can be combined with preorganization of monomers to synthesize isotactic polymer chains in the absence of a chiral auxiliary. To establish the concept, we synthesized a corannulene-substituted terphenylene monomer capable of C–H···π bonding, aromatic stacking, and van der Waals interactions. The weak intermolecular interactions steer the monomer into organized double strands, with the corannulene substituents oriented only on one side of the strand on Ag(111). A subsequent Ullmann polymerization of the self-assembled monomers leads to the formation of double-stranded isotactic polyphenylenes. The stereoregularity further allows the duplex to arrange into higher-order crystalline domains. Finally, the synthetic polymer duplex can be mechanically unzipped into individual isotactic polymer chains through scanning tunneling microscopy tip manipulation.

DOI: 10.1021/jacs.5c16884

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c16884