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 (1)H 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.