The construction of sophisticated, high-nuclearity polyhedral cages is an attractive yet challenging task in supramolecular chemistry. Herein we report the anion-coordination-driven assembly (ACDA) of a series of A2nL3n architectures ("A" denotes anion, L is ligand, n = 1, 2, 4) with a biphenylene-spaced bis-bis(urea) ligand including triple helicate A2L3 (H), tetrahedron A4L6 (T), and the octanuclear, bicapped trigonal antiprism (or parallelepiped) A8L12 (P). Among them, P is held by 96 hydrogen bonds, the largest number ever reported in a discrete polyhedron, and encapsulates multiple guests (three tetramethylammonium cations) in three compartments. Remarkably, multiple reversible transformations of these dynamic assemblies have been realized by alternation of the template guest, solvent, and concentration. Furthermore, a chiral ligand (L2S) with carbon stereocenters at both termini of the bis-bis(urea) backbone was designed and assembled with phosphate to form the enantio-pure triple helicate or tetrahedron. The chiral amplification effect in the tetrahedral complex is significantly larger than that in the triple helicate as a function of the point chirality.

中文翻译：

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基于阴离子的 A2nL3n 组件之间的多重转换：双端三角反棱镜 A8L12、四面体 A4L6 和三重螺旋 A2L3（A = 阴离子）

构建复杂的高核多面体笼是超分子化学中一项有吸引力但具有挑战性的任务。在此，我们报告了一系列 A2nL3n 结构（“A”表示阴离子，L 是配体，n = 1, 2, 4）的阴离子配位驱动组装 (ACDA) 与联苯间隔的双双（脲）配体包括三重螺旋 A2L3 (H)、四面体 A4L6 (T) 和八核双端三角反棱镜（或平行六面体）A8L12 (P)。其中，P 由 96 个氢键保持，这是有史以来在离散多面体中报道的最大数量，并将多个客体（三个四甲基铵阳离子）封装在三个隔室中。值得注意的是，这些动态组件的多次可逆转换已经通过模板客体、溶剂和浓度的交替实现。此外，在双双（脲）骨架的两个末端具有碳立体中心的手性配体（L2S）被设计并与磷酸盐组装以形成对映体纯三螺旋或四面体。作为点手性的函数，四面体复合物中的手性放大效应明显大于三螺旋中的手性放大效应。