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.
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