Programming the synthesis and self‐assembly of molecules is a compelling strategy for the bottom‐up fabrication of ordered materials. To this end, shape‐persistent macrocycles were designed with alternating carbazoles and triazoles to program a one‐pot synthesis and to bind large anions. The macrocycles bind anions that were once considered too weak to be coordinated, such as PF₆⁻, with surprisingly high affinities (β₂=10¹¹ M⁻² in 80:20 chloroform/methanol) and positive cooperativity, α=(4 K₂/K₁)=1200. We also discovered that the macrocycles assemble into ultrathin films of hierarchically ordered tubes on graphite surfaces. The remarkable surface‐templated self‐assembly properties, as was observed by using scanning tunneling microscopy, are attributed to the complementary pairing of alternating triazoles and carbazoles inscribed into both the co‐facial and edge‐sharing seams that exist between shape‐persistent macrocycles. The multilayer assembly is also consistent with the high degree of molecular self‐association observed in solution, with self‐association constants of K=300 000 M⁻¹ (chloroform/methanol 80:20). Scanning tunneling microscopy data also showed that surface assemblies readily sequester iodide anions from solution, modulating their assembly. This multifunctional macrocycle provides a foundation for materials composed of hierarchically organized and nanotubular self‐assemblies.

中文翻译：

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多功能Tricarbazolo Triazolophane大环化合物：单罐制备，阴离子结合和多层的分层自组织

对分子的合成和自组装进行编程是自下而上制造有序材料的一种引人注目的策略。为此，设计了形状持久的大环化合物，其中交替使用咔唑和三唑来编程一锅合成并结合大阴离子。曾经被认为太弱的大环化合物结合的阴离子进行协调，如PF ₆ ^- ，具有令人惊奇的高亲和力（β ₂ = 10 ¹¹ 中号^-2在80:20氯仿/甲醇）和正协同，α =（4  ķ ₂ / K ₁）= 1200。我们还发现，大环化合物在石墨表面上组装成具有分级有序管的超薄膜。使用扫描隧道显微镜观察到的显着的表面模板化自组装特性，归因于形状持久的大环之间存在的共面和边缘共享接缝中交替存在的三唑和咔唑的互补配对。多层组装还与溶液中观察到的高度分子自缔合相一致，自缔合常数为K = 300 000  M ^-1（氯仿/甲醇80:20）。扫描隧道显微镜数据还显示，表面组件易于从溶液中隔离碘化物阴离子，从而调节其组件。这种多功能大环化合物为由分层组织和纳米管自组装体组成的材料提供了基础。