Drastic Change in Incorporation of Multinuclear Complex-Cations into Hydrogen-Bonded Metallosupramolecular Frameworks Consisting of Chiral AuI3CoIII2 Complex-Anions

Chiral recognition behavior of the anionic AuI3CoIII2 complex with d-penicillaminate (d-pen), [Au3Co2(d-pen)6]3– ([1]3–), toward the cationic CoIII3 and CoIII4ZnII4 complexes with 2-aminoethanethiolate (aet), [Co3(aet)6]3+ ([2]3+) and [Co4Zn4O(aet)12]6+ ([3]6+), on crystallization is reported. Treatment of Na3[1] with the racemic (Δ)2/(Λ)2- [2](NO3)3 and (Δ)4/(Λ)4-[3]Br6 gave ionic crystals of [2][1] (I) and [3][1]2 (II), respectively. Single-crystal X-ray crystallography revealed that [1]3– anions form hydrogen-bonded frameworks with different chiral pockets that are best fitted for the accommodation of [2]3+ and [3]6+ cations in I and II, respectively. While both the (Δ)2 and (Λ)2 isomers of [2]3+ were equally incorporated in I, only the (Δ)4 isomer of [3]6+ was selectively incorporated in II.