Metallosupramolecule‐based polymeric platforms with high degrees of hierarchy and tailorable functionalities are of great interests because of their unique morphologies and potential applications. Herein, the controllable synthesis of a highly‐ordered polymeric structure, {[M,P‐Co₈(PDA)₆(HIP)₃(DMF)₅(H₂O)]₃‐[Co(DMF)(H₂O)₂]} (1) (PDA=2,6‐pyridinedicarboxylate, HIP=5‐hydroxyisophthalate, DMF=dimethylformamide) with unique topology is reported. The solid‐state structure of 1 reveals that it is alternately and periodically assembled from racemic supramolecular monomers to form a zigzag‐shaped polymeric strand. Discrete racemic supramolecules (2) with topologies similar to those of monomeric species of 1 are also controllably synthesized in a separate reaction. Formation of intermolecular hydrogen bonds between supramolecules associated with hydroxyl groups of HIPs are critical for the unique solid‐state packing geometries of 1 and 2.

中文翻译：

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由钴簇基外消旋超分子组装而成的高度有序聚合物结构的可控合成

具有高度层次性和可定制功能的基于金属超分子的聚合物平台因其独特的形态和潜在的应用而备受关注。在这里，可控合成的高阶聚合结构，{[ M，P- Co ₈（PDA）₆（HIP）₃（DMF）₅（H ₂ O）] _3- [Co（DMF）（H ₂ O ）₂ ]}（1）（PDA = 2,6-吡啶二甲酸，HIP = 5-羟基间苯二甲酸，DMF =二甲基甲酰胺），具有独特的拓扑结构。的固态结构1揭示了它是由外消旋超分子单体周期性地组装而成的，形成了锯齿形的聚合物链。具有类似于1的单体种类的拓扑的离散的外消旋超分子（2）也可在单独的反应中可控制地合成。与HIP的羟基相关的超分子之间的分子间氢键的形成对于1和2的独特固态堆积几何至关重要。