Multiple Transformations among Anion-based A2nL3n Assemblies: Bicapped Trigonal Antiprism A8L12, Tetrahedron A4L6, and Triple Helicate A2L3 (A = Anion)

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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 A 2 n L 3 n architectures (“A” denotes anion, L is ligand, n = 1, 2, 4) with a biphenylene-spaced bis - bis (urea) ligand including triple helicate A 2 L 3 ( H ), tetrahedron A 4 L 6 ( T ), and the octanuclear, bicapped trigonal antiprism (or parallelepiped) A 8 L 12 ( 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 ( L 2 S ) 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.