Crystal engineering of 2-D and 3-D multiporphyrin architectures - The versatile topologies of tetracarboxyphenylporphyrin-based materials

This study explores diverse crystal engineering concepts in the formulation of a series of new porphyrin-based supramolecular arrays, utilizing tetrak is(4-carboxyphenyl)porphyrin as an effective building block. Different mode s of the supramolecular assembly are demonstrated. They include: (a) self-a ssembly of the porphyrin units into extended networks through multiple. hyd rogen bonding, (b) intermolecular coordination assisted by external sodium ion auxiliaries which link between the carboxylic/carboxylate groups of sev eral units, (c) formation of coordination polymers with the aid of bidentat e ligands as bridges between the metal centers of the porphyrin molecules, and (d) various combination motifs of concerted hydrogen bonding and coordi nation features, The resulting multiporphyrin architectures obtained in thi s study illustrate the expression of several motifs (synthons) of noncovale nt interaction in the construction of network solids, which can be potentia lly useful in the design of new porphyrin-based materials with attractive p roperties.