Methylazacalixpyridines: Remarkable Bridging Nitrogen-Tuned Conformations and Cavities with Unique Recognition Properties

• Published in: Chemistry : a European journal Vol. 12; no. 36; pp. 9262 - 9275
• Main Authors: Gong, Han-Yuan, Zhang, Xiao-Hang, Wang, De-Xian, Ma, Hong-Wei, Zheng, Qi-Yu, Wang, Mei-Xiang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 13.12.2006; WILEY‐VCH Verlag; Wiley
• Subjects: anion recognition; azacalixarenepyridines; azacalixpyridines; cavity; Chemistry; Chemistry, Multidisciplinary; conformation; fullerenes; Physical Sciences; Science & Technology; azacalixarenepyridines; anion recognition; CRYSTAL-STRUCTURE; conformation; fullerenes; SULFUR; cavity; PORPHYRIN; FURAN; aza-calixpyridines; CONDENSATION; C-60; COMPLEXATION; EFFICIENT; ANION-BINDING; CALIXARENES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200600377

Methylazacalix[n]pyridines (n = 4, 8) and methylazacalix[m]arene[n]pyridines (m = n = 2, 4) have been synthesized by a convenient fragment coupling approach starting from 2,6‐dibromopyridine, 2,6‐diaminopyridine, and benzene‐1,3‐diamine. Thanks to the intrinsic electronic nature of nitrogen, which can adopt mainly sp2 hybridization, allowing it variously to conjugate, partially conjugate, or not conjugate with the adjacent one or two pyridine rings, the resulting nitrogen‐bridged calixpyridine derivatives act as a unique class of macrocyclic host molecules with intriguing conformational structures offering fine‐tunable cavities and versatile recognition properties. Whilst in solution it is fluxional, in the solid state methylazacalix[4]pyridine adopts a 1,3‐alternate conformation with a C2v symmetry in which every two bridging nitrogen atoms conjugate with one pyridine ring. After protonation, the methylazacalix[4]pyridinium species has a different conjugation system of its four bridging nitrogen atoms, yielding the similar twisted 1,3‐alternate conformations with an approximate S4 symmetry. The cavity of each protonated methylazacalix[4]pyridine, however, varies finely to accommodate guest species of different size and geometry, such as planar DMF or HO2CCO2− ion, a twisted HO2CCO2− ion, and a tetrahedral ClO4− ion. As giant macrocyclic hosts, both methylazacalix[8]pyridine and methylazacalix[4]arene[4]pyridine interact efficiently with fullerenes C60 and C70 through van der Waals forces. Their ease of preparation, versatile conformational structures, and recognition properties make these multinitrogen‐containing calixarenes or cyclophanes unique and powerful macrocyclic hosts in supramolecular chemistry. Unique and powerful supramolecular macrocyclic hosts: Methylazacalix[n]pyridines (n = 4, 8) and methylazacalix[m]arene[n]pyridines (m = n = 2, 4) have been synthesized by a convenient fragment coupling approach starting from 2,6‐dibromopyridine, 2,6‐diaminopyridine, and benzene‐1,3‐diamine. Thanks to the intrinsic electronic nature of nitrogen, the resulting nitrogen‐bridged calixpyridine derivatives act as a unique class of macrocyclic host molecules with intriguing conformational structures offering fine‐tunable cavities and versatile recognition properties.