Muniappan Sankar, Lipstman Sophia, George Sumod, Goldberg Israel
School of Chemistry, Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat-Aviv, Tel-Aviv 69978, Israel.
Inorg Chem. 2007 Jul 9;46(14):5544-54. doi: 10.1021/ic0701099. Epub 2007 Jun 13.
New types of porphyrin-based framework solids were constructed by reacting meso-tetra(3-carboxyphenyl)porphyrin and meso-tetra(4-carboxyphenyl)metalloporphyrins with common salts of lanthanide metal ions. The large size, high coordination numbers and strong affinity for oxo ligands of the latter, combined with favorable hydrothermal reaction conditions, allowed the formation of open three-dimensional single-framework architectures by coordination polymerization, in which the tetradentate porphyrin units are intercoordinated by multinuclear assemblies of the bridging metal ions. The latter serve as construction pillars of the supramolecular arrays, affording stable structures. Several modes of coordination polymerization were revealed by single-crystal X-ray diffraction. They differ by the spatial functionality of the porphyrin building blocks, the coordination patterns of the lanthanide-carboxylate assemblies, and the topology of the resulting frameworks. The seven new reported structures exhibit periodically spaced 0.4-0.6 nm wide channel voids that perforate the respective crystalline polymeric architectures and are accessible to solvent components. Materials based on the m-carboxyphenyl derivative reveal smaller channels than those based on the p-carboxyphenyl analogues. An additional complex of the former with a smaller third-row transition metal (Co) is characterized by coordination connectivity in two dimensions only. Thermal and powder-diffraction analyses confirm the stability of the lanthanide-TmCPP (TmCPP=tetra(m-carboxyphenyl)porphyrin) frameworks.
通过使中位-四(3-羧基苯基)卟啉和中位-四(4-羧基苯基)金属卟啉与镧系金属离子的常见盐反应，构建了新型的基于卟啉的骨架固体。后者的大尺寸、高配位数以及对氧配体的强亲和力，再结合有利的水热反应条件，使得通过配位聚合形成开放的三维单骨架结构成为可能，其中四齿卟啉单元通过桥连金属离子的多核组装体相互配位。后者作为超分子阵列的构建支柱，提供稳定的结构。单晶X单晶射线单晶衍射揭示了几种配位聚合模式。它们在卟啉结构单元的空间功能、镧系羧酸盐组装体的配位模式以及所得骨架的拓扑结构方面存在差异。所报道的七种新结构呈现出周期性间隔的0.4 - 0.6 nm宽的通道空隙，这些空隙贯穿各自的晶体聚合物结构并且溶剂成分可以进入。基于间羧基苯基衍生物的材料显示出比基于对羧基苯基类似物的材料更小的通道。前者与一种较小的第三周期过渡金属（钴）形成的额外配合物仅在二维上具有配位连接性。热分析和粉末衍射分析证实了镧系-TmCPP（TmCPP = 四(间羧基苯基)卟啉）骨架的稳定性。
