While oxidized pillar[5]arenes with 1-5 benzoquinone units are known, very few examples of oxidized pillar[6]arenes have been reported. We describe here the synthesis, characterization and electrochemical behavior of a series of macrocyclic hosts prepared by the stepwise oxidation of 1,4-diethoxypillar[6]arene, resulting in high-yield and high-purity isolation of two constitutional isomers for each macrocycle, in which two, three or four 1,4-diethoxybenzene units are replaced by benzoquinone residues. A careful structural comparison with their counterparts in the pillar[5]arene framework indicates that the geometries of the macrocycles are better described as non-Euclidean hyperbolic hexagons and elliptic pentagons, respectively. A comprehensive computational study to determine anisotropic induced current density (ACID) allows us to visualize and quantify through-space and through-bond communication pathways along the macrocyclic belt. Experimental and simulated voltammetric data, as well as UV-vis spectra, of the new macrocycles afford insights into the various electronic communication pathways in these compounds.

虽然已知具有 1-5 个苯醌单元的氧化柱 [5] 芳烃，但很少有氧化柱 [6] 芳烃的例子被报道。我们在这里描述了通过 1,4-二乙氧基柱 [6] 芳烃的逐步氧化制备的一系列大环主体的合成、表征和电化学行为，导致每个大环的两种结构异构体的高产率和高纯度分离，其中两个、三个或四个 1,4-二乙氧基苯单元被苯醌残基取代。与柱 [5] 芳烃框架中的对应物进行仔细的结构比较表明，大环的几何形状最好分别描述为非欧几里德双曲六边形和椭圆五边形。一项确定各向异性感应电流密度 (ACID) 的综合计算研究使我们能够可视化和量化大环带上的空间和键间通信路径。新大环化合物的实验和模拟伏安数据以及紫外-可见光谱提供了对这些化合物中各种电子通信路径的深入了解。