Crystal Engineering of 2-D and 3-D Multiporphyrin Architectures − The Versatile Topologies of Tetracarboxyphenylporphyrin-Based Materials

Abstract

This study explores diverse crystal engineering concepts in the formulation of a series of new porphyrin-based supramolecular arrays, utilizing tetrakis(4-carboxyphenyl)porphyrin as an effective building block. Different modes of the supramolecular assembly are demonstrated. They include: (a) self-assembly of the porphyrin units into extended networks through multiple hydrogen bonding, (b) intermolecular coordination assisted by external sodium ion auxiliaries which link between the carboxylic/carboxylate groups of several units, (c) formation of coordination polymers with the aid of bidentate ligands as bridges between the metal centers of the porphyrin molecules, and (d) various combination motifs of concerted hydrogen bonding and coordination features. The resulting multiporphyrin architectures obtained in this study illustrate the expression of several motifs (synthons) of noncovalent interaction in the construction of network solids, which can be potentially useful in the design of new porphyrin-based materials with attractive properties.