A general and high yielding fragment coupling synthesis of heteroatom-bridged calixarenes and the unprecedented examples of calixarene cavity fine-tuned by bridging heteroatoms

A number of aza- and/or oxo-bridged calix[2]arene[2]triazines have been synthesized through an unusually high yielding and efficient fragment coupling approach starting from cyanuric chloride and resorcinol, 3-aminophenol, m-phenylenediamine, and N,N-dimethyl-m-phenylenediamine. These novel macrocycles, which belong to the next generation of calixarenes or cyclophanes, form a unique cavity that is resulted from two isolated benzene planes and two bis-heteroatom-conjugated triazine planes in a 1,3-alternate fashion. The nature of the bridging heteroatoms, i.e., combination of the electronic, conjugative, and steric effects of the nitrogen and oxygen atoms, strongly regulates the cavity size, generating a set of fine-tuned cavities in which the distance between two benzene rings at the upper rim ranges from 5.011 to 7.979 A. The multiple intermolecular hydrogen bond interactions among N,N-dimethylated tetraazacalix-[2]arene[2]triazines and among tetraazacalix[2]arene[2]triazines lead to the formation of infinite one-dimensional chain structure and two-dimensional zigzag layered structure, respectively, in the solid state. The ease of preparation and further chemical manipulations, and the readily tunable cavity structures render these aza- and/or oxo-bridged calix[2]arene[2]triazines the unique platforms in the study of supramolecular chemistry.