Control of the spatial arrangements of supramolecular networks based on saddle-distorted porphyrins by intermolecular hydrogen bonding

Supramolecular integration of a saddle-distorted zinc(II) porphyrin complex, which has hydroxyl groups at the para-position of the four meso-aryl groups, has been demonstrated on the basis of hydrogen bonding among the peripheral hydroxyl groups. The hydrogen-bonding patterns were controlled by the recrystallization solvents and additives, and particularly, addition of a bifunctional ligand such as 4,4'-bipyridine (bpy). The coordination of bpy to form dinuclear Zn(II)-porphyrin complexes causes a conformational difference: the dimeric complex with four hydroxyl groups is in an eclipsed form, however, a derivative without hydroxyl groups is in a staggered form due to the presence or absence of the intermolecular hydrogen bonding. In addition, the dimerization by the bpy coordination resulted in the expansion of the intermolecular space formed in the porphyrin networks, suggesting the potential to be applied for inclusion of guest molecules.