Two macrotricyclic ligands composed of two face-to-face octadentate metal chelates were synthesized. These cage-shaped disodium complexes had special recognition ability for various counter anions. Specific chiral dicarboxylates bound to the complexes within the cavity and exhibited chirality induction properties. For instance, N-Boc-Asp dianion strongly induced circular dichroism (CD) signals, but N-Boc-Glu dianion, which is one carbon longer, did not.

A series of quadruple-stranded Na⁺ and Ca²⁺ complexes with octadentate cyclen ligands was synthesized to produce complexes that contained four different side-arm combinations (one triazolecoumarin group and three pyridine groups (1), four pyridine groups (2), one triazolecoumarin group and three quinoline groups (3), and four quinoline groups (4)). X-ray crystallographic analysis revealed that no significant changes occurred in the stereostructure of these complexes upon replacing one pyridine group with a triazolecoumarin moiety, or by replacing Na⁺ ions with Ca²⁺ ions, although the coordination number of the complexes in the solid state decreased when pyridine groups were replaced by quinoline groups. In solution, all of the side arms were arranged in a propeller-like pattern to yield an enantiomer pair of Δ and Λ forms in each metal complex. The addition of a tert-butoxycarbonyl (Boc)-protected amino acid anion, that is, a coordinative chiral carboxylate anion, to the cyclenCa²⁺ complex induced circular dichroism (CD) signals in the aromatic region by forming a 1:1 mixture of diastereomeric ternary complexes with opposite complex chirality, whilst the corresponding Na⁺ complexes rarely showed any response. In complexes 1-Ca²⁺ and 3-Ca²⁺, this chirality-transfer process was efficiently followed by considering the induction of the CD signals at two different wavelengths, that is, the coumarin-chromophore region and the aza-aromatic region. The sign and intensity of the CD signal were significantly dependent on both the nature of the aza-aromatic moiety and the enantiomeric purity of the external anion. These Ca²⁺ complexes worked as effective probes for the determination of the enantiomeric excess of the chiral anion. The cyclenCa²⁺ complexes also interacted with the non-coordinative Δ-TRISPHAT anion through an ion-pairing mechanism to achieve chirality transfer from the anion to the metal complex; both complexes 1-Ca²⁺ and 3-Ca²⁺ clearly showed induced CD signals in the coumarin-chromophore region, owing to ion-paring interactions with the Δ-TRISPHAT anion. Thus, the proper combination of an octadentate cyclen ligand and a metal center demonstrated effective chirality transfer.