The development of precise folding techniques for synthetic polymer chains that replicate the unique structures and functions of biopolymers has long been a key challenge. In particular, spiro-type (i.e., 8-, trefoil-, and quatrefoil-shaped) polymer topologies remain challenging due to their inherent structural complexity. Herein, we establish a folding strategy to produce spiro-type multicyclic polymers via intramolecular ring-opening metathesis oligomerization of the norbornenyl groups attached at predetermined positions along a synthetic polymer precursor. This strategy provides easy access to the desired spiro-type topological polymers with a controllable number of ring units and molecular weight while retaining narrow dispersity (Ɖ < 1.1). This effective strategy marks an advancement in the development of functionalized materials composed of specific three-dimensional nanostructures.

长期以来，为复制生物聚合物独特结构和功能的合成聚合物链开发精确折叠技术一直是一项关键挑战。特别是，螺型（即 8 型、三叶型和四叶型）聚合物拓扑结构由于其固有的结构复杂性而仍然具有挑战性。在此，我们建立了一种折叠策略，通过连接在合成聚合物前体预定位置的降冰片烯基的分子内开环复分解低聚反应来生产螺型多环聚合物。该策略可轻松获得所需的螺型拓扑聚合物，其环单元数和分子量可控，同时保持窄分散性（Ɖ < 1.1)。这种有效的策略标志着由特定三维纳米结构组成的功能化材料的开发取得了进步。