A General and High Yielding Fragment Coupling Synthesis of Heteroatom-Bridged Calixarenes and the Unprecedented Examples of Calixarene Cavity Fine-Tuned by Bridging Heteroatoms

• Published in: Journal of the American Chemical Society Vol. 126; no. 47; pp. 15412 - 15422
• Main Authors: Wang, Mei-Xiang, Yang, Hai-Bo
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.12.2004; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Organic chemistry; Organic compounds; Physical Sciences; Physics; Preparations and properties; Science & Technology; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; RECOGNITION; ASSEMBLIES; MACROCYCLES; STRATEGY; HYBRID; CYANURIC CHLORIDE; ANION-BINDING; WATER; Organic synthesis; Molecular packing; Molecular structure; Nitrogen heterocycle; Macrocyclization; Molecular interaction; Calixarene; Oxygen heterocycle; X ray diffraction; Chemical coupling; Hydrogen bond; Crystalline structure
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0465092

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 Å. 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.