Resolution of Chiral, Tetrahedral M4L6 Metal−Ligand Hosts1

The supramolecular metal-ligand assemblies of M416 stoichiometry are chiral (M = GaIII, AlIII, InIII, FeIII, TiIV, or GeIV, H41 = N,N'-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene). The resolution process of delta delta delta delta- and lambda lambda lambda lambda-M(4)1(6)12- by the chiral cation S-nicotinium (S-nic+) is described for the Ga(III), Al(III), and Fe(III) assemblies, and the resolution is shown to be proton dependent. From a methanol solution of M(acac)3, H(4)1, S-nicI, and KOH, the delta delta delta delta-KH3(S-nic)7(S-nic) subset M(4)1(6) complexes precipitate, and the lambda lambda lambda lambda-K6(S-nic)5(S-nic) subset M(4)1(6) complexes subsequently can be isolated from the supernatant. Ion exchange enables the isolation of the (NEt4(+))(12), (NMe4(+))(12), and K+(12) salts of the resolved structures, which have been characterized by CD and NMR spectroscopies. Resolution can also be accomplished with 1 equiv of NEt4+ blocking the cavity interior, demonstrating that external binding sites are responsible for the difference in S-nic+ enantiomer interactions. Circular dichroism data demonstrate that the (NMe4(+))(12) and (NEt4(+))(12) salts of the resolved Ga(4)1(6)12- and Al(4)1(6)12- structures retain their chirality over extended periods of time (>20 d) at room temperature; heating the (NEt4(+))(12)Ga(4)1(6) assembly to 75 degrees C also had no effect on its CD spectrum. Finally, experiments with the resolved K(12)Ga(4)1(6) assemblies point to the role of a guest in stabilizing the resolved framework.