Multicomponent Assembly of Macrocycles and Polymers by Coordination of Pyridyl Ligands to 1,4‐Bis(benzodioxaborole)benzene

Abstract Multicomponent reactions between 1,4‐benzenediboronic acid, catechol, and different pyridyl ligands are reported. The condensation of 1,4‐benzenediboronic acid with catechol gives 1,4‐bis(benzodioxaborole)benzene. Upon crystallization, the ester aggregates with the N‐donor ligands through dative BN bonds. Depending on the nature of the pyridyl ligand, molecularly defined macrocycles or polymeric structures are obtained. 1D polymers are formed with 4,4‐bipyridine and 1,2‐di(4‐pyridyl)ethylene, whereas a 2D network is obtained with the tetradentate ligand tetra(4‐pyridylphenyl)ethylene. These results highlight the utility of dative BN bonds in structural supramolecular chemistry and crystal engineering.