清华大学王梅祥团队近日研究了杯芳烃大掺氮锯齿形烃带的合成、结构和性能。2025年5月26日出版的《德国应用化学》杂志发表了这项成果。

锯齿形烃带和掺杂杂原子的类似物因其独特的结构、诱人的性质和潜在的应用而吸引了化学家。尽管合成技术取得了突破，但通过峡湾拼接方法合成的带的多样性，特别是带的大小，受到间苯二酚[n]芳烃（n=4,6）的限制。研究组报道了以常规杯[8]芳烃为原料的大带的合成、结构和性能。 

该合成的特点是全溴杯[8]芳烃与苯胺和氨的多个C-N交叉偶联反应，以及1,4-二氢喹啉选择性转化为喹啉-4（1H）-酮链段。所讨论的分子采用独特的锯齿带结构，氮原子和官能团位于两个入口周围，形成一个巨大的八角棱柱腔。它们能够以高亲和力容纳富勒烯C₆₀或C₇₀，这是由孤对电子/π相互作用和主体与客体之间的空间互补性驱动的。

附：英文原文

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

Author: Mei-Xiang Wang, Yi Peng, Mei-Ling Tan, Ke-Xing Ma, Shuo Tong

Issue&Volume: 2025-05-26

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(1H)-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 C60 or C70 with high affinity driven by lone-pair electron/π interactions and steric complementarity between host and guest.

DOI: 10.1002/anie.202509916

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202509916