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首页> 外文期刊>Crystal growth & design >Coordination Polymers of Tetra(4-carboxyphenyl)porphyrins Sustained by Tetrahedral Zinc Ion Linkers
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Coordination Polymers of Tetra(4-carboxyphenyl)porphyrins Sustained by Tetrahedral Zinc Ion Linkers

机译：四面体锌离子接头保持的四（4-羧基苯基）卟啉配位聚合物

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摘要

Reactions between the free base tetra(4-carboxyphenyl)porphyrin and the corresponding platinum or palladium metalloporphyrin derivatives with zinc acetate dihydrate under solvothermal conditions in a basic environment (in the presence of pyridine and ammonium hydroxide) yielded extended supramolecular networks. These polymeric arrays consist of fully deprotonated porphyrin carboxylate units interconnected to each other by Zn(H_2O)_2~(2+) auxiliaries. The zinc ion linkers adapt a tetrahedral coordination environment, imparting to the polymeric network an open three-dimensional architecture, wherein each zinc binds to two adjacent porphyrin units and two water ligands, while every porphyrin entity is linked to four different metal centers. In a reaction involving the free base macrocycle, the zinc ions were inserted into the porphyrin core as well, forming a five-coordinate entity with pyridine as an axial ligand. The solid state syntheses yielded either one-dimensional ladder type coordination polymers that pair in an interlocking manner or three-dimensional diamondoid arrangements with interpenetrating polymeric networks. Both types of frameworks are further interlinked to each other by weak hydrogen bonds from the zinc-bound water ligands of one array to the carboxylate functions of another. The previously reported porphyrin-based polymer tessellated by Zn~(2+) linkers that coordinate at a given binding site to four (rather than two) porphyrin units is also discussed.
机译：游离碱四（4-羧基苯基）卟啉与相应的铂或钯金属卟啉衍生物与乙酸锌二水合物在溶剂热条件下，在碱性环境中（在吡啶和氢氧化铵存在下）反应，产生扩展的超分子网络。这些聚合物阵列由通过Zn（H_2O）_2〜（2+）助剂相互连接的完全去质子化的卟啉羧酸酯单元组成。锌离子接头适应四面体配位环境，使聚合物网络具有开放的三维结构，其中每个锌与两个相邻的卟啉单元和两个水配体结合，而每个卟啉实体均与四个不同的金属中心相连。在涉及游离碱大环的反应中，锌离子也被插入到卟啉核中，以吡啶作为轴向配体形成五配位实体。固态合成产生以互锁方式配对的一维阶梯型配位聚合物或具有互穿聚合物网络的三维菱形排列。两种类型的骨架还通过弱氢键从一个阵列的与锌结合的水配体到另一个阵列的羧酸酯官能团相互连接。还讨论了以前报道的由Zn〜（2+）接头镶嵌的卟啉基聚合物，该接头在给定的结合位点与四个（而不是两个）卟啉单元进行配位。

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