Synthesis, characterisation and X-ray structure of a novel porphyrin array employing Zn–O and O–H…O bonding motifs

The preparation and characterisation of the free-base and zinc metallated derivatives of 5,10,15,20-tetrakis(4-(2-(2-hydroxyethoxy)ethoxy)phenyl)porphyrin 1 is described. The X-ray crystal structure of the Zn(II) adduct 2 dimerises in the solid state via an intermolecular polyether oxygen–Zn(II) interaction (O…Zn = 2.124(4) Å). The porphyrin dimers form discrete layers defined by a distance of 5.10 Å between the porphyrin planes in adjacent layers. A bilayer sheeting arrangement of the porphyrin macrocyclic units is achieved through cooperative hydrogen bonding of the ethoxyethanol arms to form 11-membered macrocycles containing four hydrogen bonds.

Graphical abstractThe crystal structure of 2 dimerises in the solid state (shown schematically) via an intermolecular polyether oxygen–Zn(II) interaction to form a 28-membered macrocycle. A bilayer sheeting arrangement of the dimers is achieved through cooperative hydrogen bonding of the ethoxyethanol arms to form 11-membered macrocycles containing four hydrogen bonds.Figure optionsDownload full-size imageDownload as PowerPoint slide