Self-Assembly of Functionalized Metalloporphyrins into Microporous Polymeric Networks

Abstract This study deals with the preparation and structural characterization of crystalline assemblies based on the tetra(4-cyanophenyl), tetra(4-nitrophenyl) and tetra(4-amidophenyl) derivatives of metallated porphyrin as building blocks, toward the design of novel coordination polymers and microporous organic solids. The cyanophenyl derivative forms under selected conditions two-dimensional coordination polymers through direct ligation of the-CN functions to the metal centers of neighboring porphyrins. In most other cases it self-assembles into layered multiporphyrin arrays which consist of uniquely structured supramolecular chains and networks with large cavities. Similar intermolecular architectures were observed in solids based on the nitrophenyl and amidophenyl porphyrin entities. The layered organization in these materials is dominated to a large extent by molecular shape and aromaticity of the porphyrin frameworks, while its porous nature is sustained and controlled by non-covalent interactions ...