We have investigated the hydrogen bond-driven assembly of nickel and freebase tetra(carboxyphenyl) and tetra(carboxylatophenyl) porphyrins. When the tetracarboxylates were crystallized with bis(amidinium) species, their crystal structures contained a range of hydrogen bond geometries, and we did not obtain well-ordered networks. Use of a tetrahedral tetra(amidinium) building block yielded a 3D framework material with a PtS topology, which contains only a “paired” hydrogen bonding arrangement. This framework is highly porous, with ∼3/4 of the unit cell volume occupied by disordered solvent molecules, although it loses crystallinity upon removal from solvent. Favourable interactions between porphyrin carboxylic acid hydrogen bond donors and bipyridine nitrogen atoms were then used to prepare a stable 2D porphyrin grid-like network.

中文翻译：

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基于5,10,15,20-四（4-羧苯基）卟啉的超分子构架†

我们已经研究了镍和游离碱四（羧苯基）和四（羧甲基苯基）卟啉的氢键驱动组装。当四羧酸盐与双（ami）类结晶时，它们的晶体结构包含一定范围的氢键几何形状，我们没有获得有序的网络。使用四面体四（ami）结构单元可生成具有PtS拓扑的3D框架材料，其中仅包含“成对的”氢键排列。这种骨架是高度多孔的，尽管无序溶剂分子会失去结晶性，但约有单元细胞体积的3/4占据。然后使用卟啉羧酸氢键供体与联吡啶氮原子之间的良好相互作用来制备稳定的二维卟啉网格状网络。