Self-assembly of porphyrin hexamers via bidentate metal–ligand coordination

Abstract

The supramolecular assembly of metal-porphyrin hexamers with bidentate ligands in chloroform solutions is demonstrated by UV/Vis and ¹H NMR-titrations, and Small Angle Neutron Scattering (SANS) experiments. Titrations of zinc porphyrin hexamer Zn1 with 1,4-diazabicyclo[2,2,2]octane (DABCO) revealed that at a DABCO/Zn1 molar ratio of 3, intermolecular sandwich complexes are formed, which can be considered as “circular-shaped porphyrin ladders”. These supramolecular complexes further aggregate into larger polymeric stacks, as a result of a combination of cooperativity effects, π–π stacking interactions, and chelate effects. The presence of rodlike assemblies in solution, formed by assembly of Zn1 and DABCO, is confirmed by SANS-experiments. Using a model for cylindrical assemblies, curve fitting calculations reveal that rods with an average length of 26 nm and a radius of 30–35 Å were formed, corresponding to columnar stacks of approximately 30 hexamer molecules. In contrast, the metal-free hexamer H₂1 did not form extended assemblies due to the absence of coordinative intermolecular interactions.