In recent years, synthesis of hybrid heteroarm star polymer with precisely defined arms has evolved to be one of the most attractive topics within polymer chemistry. In this study, we present the successful synthesis of metallacycle‐linked heteroarm star polymers (HASPs) composed of crystalline poly(ε‐caprolactone) (PCL) and polyacrylate (poly (N‐isopropylacrylamide) (PNIPAM) segments via combination of ring‐opening polymerization (ROP) and reversible addition‐fragmentation chain transfer (RAFT) controlled radical polymerization. Firstly, a hexagonal metallacycle containing three hydroxy groups and three chain transfer agent moieties at the alternative vertexes was designed and synthesized based on the general principle of coordination‐driven self‐assembly. Subsequently, upon combination of two orthogonal post‐assembly polymerizations, a new family of HASPs containing a well‐defined hexagonal metallacycle with precisely controlled position of polymer arms was facilely prepared. Interestingly, the obtained HASPs could spontaneously self‐assemble into large‐area and regular cubic nanoparticles in tetrahydrofuran (THF)/methanol (MeOH) mixed solvents under specific conditions as confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). This study provides a simple route to the controllable preparation of HASPs, and opens up a new way for further study on self‐assembly of different HASPs systems.

中文翻译：

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通过正交组装后聚合反应构建金属环连接的杂原子星形聚合物，以及将其有趣地自我组装成大面积和规则的纳米立方体†

近年来，具有精确定义的臂的杂化杂星聚合物的合成已发展成为聚合物化学领域中最有吸引力的主题之一。在这项研究中，我们提出结晶聚组成金属环连接的杂臂星形聚合物（搭扣）（成功合成ε己内酯）（PCL）和聚丙烯酸酯（聚（Ñ -isopropylacrylamide）（PNIPAM）链段通过开环聚合（ROP）和可逆加成-断裂链转移（RAFT）控制的自由基聚合相结合。首先，根据配位驱动自组装的一般原理，设计并合成了一个在替代顶点处包含三个羟基和三个链转移剂部分的六角金属环。随后，将两种正交的组装后聚合反应结合在一起，即可轻松制得一个新的HASP系列，其中包含定义明确的六角形金属环，并精确控制了聚合物臂的位置。有趣的是 扫描电子显微镜（SEM）和原子力显微镜（AFM）证实，在特定条件下，所获得的HASP可以在四氢呋喃（THF）/甲醇（MeOH）混合溶剂中自组装成大面积且规则的立方纳米颗粒。这项研究为可控HASP的制备提供了一条简单的途径，并为进一步研究不同HASP系统的自组装开辟了一条新途径。