In this report, a new series of mono‐, di‐, tri‐, and tetra‐cationic pyridinium and vinyl pyridinium‐modified [2.2]paracyclophanes as useful molecular tectons for supramolecular systems are described. Regioselective functionalization at specific positions, followed by resolution step and successive transformations through Pd‐catalyzed Suzuki‐Miyaura and Mizoroki‐Heck cross‐coupling chemistry furnish a series of modular PCP scaffolds. In our proof‐of‐concept study, on N‐methylation, the PCPs bearing (cationic) pyridyl functionalities were demonstrated as useful molecular receptors in host‐guest supramolecular assays. The PCPs on grafting with light‐responsive azobenzene (−N=N−) functional core as side‐groups impart photosensitivity that can be remotely transformed on irradiation, offering photo‐controlled smart molecular functions. Furthermore, the symmetrical PCPs bearing bi‐, and tetra‐pyridyl functionalities at the peripheries have enormous potential to serve as ditopic and tetratopic 3D molecular tectons for engineering non‐covalent supramolecular assemblies with new structural and functional attributes.

中文翻译：

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单、二、三和四阳离子吡啶鎓和乙烯基吡啶鎓改性[2.2]对环芳烷的合成：超分子系统的模块化受体

在本报告中，描述了一系列新的单、二、三和四阳离子吡啶鎓和乙烯基吡啶鎓改性的[2.2]对环芳烷作为超分子系统的有用分子构造。在特定位置进行区域选择性功能化，然后通过 Pd 催化的 Suzuki-Miyaura 和 Mizoroki-Heck 交叉偶联化学进行解析步骤和连续转化，提供了一系列模块化 PCP 支架。在我们的概念验证研究中，氮‐甲基化后，带有（阳离子）吡啶基官能团的 PCP 被证明是主客体超分子测定中有用的分子受体。PCP 接枝光响应偶氮苯 (−N=N−) 功能核作为侧基，赋予光敏性，可在照射下远程转化，提供光控智能分子功能。此外，在外围具有双和四吡啶基官能团的对称PCP具有作为双位和四位3D分子构造的巨大潜力，用于工程具有新结构和功能属性的非共价超分子组装体。