Supramolecular porphyrin-based materials. Assembly modes of [5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrinato]zinc with bipyridyl ligands

Reaction of [5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrinato]zinc with bipyridyl-type ligands leads to the formation of extended three-dimensional supramolecular architectures sustained by a concerted mechanism of metal-ligand (pyridyl-N⋯Zn) coordination and cooperative intermolecular (O-H⋯OH and O-H⋯N) hydrogen bonding. The competing nature of these interactions, along with the different length and functionality of the ligand auxiliaries, affects the resulting motifs of the porphyrin-ligand supramolecular assembly. Herein we describe new heterogeneous complexes of this type, and evaluate the various modes of intermolecular association in these materials.