Large N‐Doped Zigzag Hydrocarbon Belts from Calixarenes: Synthesis, Structure, and Properties

Abstract

Abstract Zigzag hydrocarbon belts and heteroatom‐doped analogs have captivated chemists because of their unique structures, tantalizing properties, and potential applications. Despite synthetic breakthroughs, the diversity, especially, the size of belts synthesized by fjord‐stitching approach is limited by resorcin[n]arenes ( n  = 4, 6). We report herein the synthesis, structure and properties of large belts starting from conventional calix[8]arenes. The synthesis features multiple C─N cross‐coupling reactions of per‐brominated calix[8]arenes with anilines and ammonia, and selective transformation of 1,4‐dihydroquinoline into quinolin‐4(1 H )‐one segments. The molecules in question adopt a unique zigzag belt structure with nitrogen atoms and functional groups located around both portals, yielding a large octagonal prism cavity. They are able to accommodate fullerene C 60 or C 70 with high affinity driven by lone‐pair electron/π interactions and steric complementarity between host and guest.