近日，德国马尔堡菲利普斯大学J.Michael Gottfried团队报道了表面自由基开环聚合产生超长聚（对苯基），以获得非苯类碳纳米带。2026年3月16日出版的《自然-化学》杂志发表了这项成果。

延长未取代聚对苯撑（PPP）等导电聚合物的链长，对其在高性能有机器件中的应用及加工成高质量功能材料至关重要。尽管表面辅助的乌尔曼偶联已将PPP链长从溶液反应的约32纳米提升至约100纳米，但其逐步增长反应机制限制了链长的进一步延伸。

研究组报道了在铜(111)表面通过[6]环对苯撑自由基开环聚合合成PPP的研究。该过程被证实为链增长聚合，使PPP链长显著延长至微米范围（约0.9微米）。所得超长PPP链在洁净表面上发生选择性碳氢键断裂，形成直立的聚对苯炔中间体，该中间体进一步偶联形成长度达约40纳米的未取代联苯烯纳米带。开环聚合为高质量聚合物及具有精确结构可控性的非苯型碳纳米带的制备提供了一条通用途径。

附：英文原文

Title: On-surface radical ring-opening polymerization produces ultralong poly(para-phenylene) for access to non-benzenoid carbon nanoribbons

Author: Fan, Qitang, Zhong, Qigang, Luy, Jan-Niclas, Schramm, Jakob, Ruppenthal, Lukas, Leng, Wenhui, Ebeling, Daniel, Tonner-Zech, Ralf, Schirmeisen, Andr, Gottfried, J.Michael

Issue&Volume: 2026-03-16

Abstract: Extending the chain lengths of conductive polymers, such as unsubstituted poly(para-phenylene) (PPP), is crucial for their application in high-performance organic devices and processing into high-quality functional materials. While surface-assisted Ullmann coupling has increased PPP chain lengths to ~100nm, from ~32nm achieved by solution-based reactions, its step-growth reaction mechanism limits further elongation. Here we report the synthesis of PPP via radical ring-opening polymerization of [6]cyclo(para-phenylene) on a Cu(111) surface. This process has been identified as a chain-growth polymerization, substantially enhancing the PPP chain length to the micrometre range (~0.9 μm). The obtained ultralong PPP chains on an otherwise clean surface undergo selective C–H bond scission, forming an upright-standing poly(para-benzyne) intermediate, which further couples into the unsubstituted biphenylene ribbon with length up to ~40nm. The ring-opening polymerization provides a versatile route to high-quality polymers and non-benzenoid carbon nanoribbons with precise structural control.

DOI: 10.1038/s41557-026-02092-y

Source: https://www.nature.com/articles/s41557-026-02092-y