Cooperative assembly of H-bonded rosettes inside a porphyrin nanoring

The melamine·barbiturate H-bonded rosette motif is of comparable dimensions and symmetry to the cavity of a butadiyne-linked 6-porphyrin nanoring. Functionalisation of each of the barbiturate components and the pyrimidine components of a H-bonded rosette with a pyridine ligand leads to a self-assembled hexapyridine ligand, which binds cooperatively to the zinc porphyrin nanoring. UV-vis-NIR and ¹H NMR experiments show that the 7-component assembly forms at concentrations at which neither the H-bonding interactions nor the zinc porphyrin-pyridine interactions are formed in the absence of one of the three components. The mean effective molarities of these rosette complexes are around 200 mM in chloroform at 298 K.