Stabilization of Octahedral Metal Halide Clusters by Host-Guest Complexation with γ-Cyclodextrin: Toward Nontoxic Luminescent Compounds

Abstract

γ-Cyclodextrin (γ-CD) interacts in aqueous solution with octahedral halide clusters Na₂[{M₆X₈}Cl₆] (M = Mo, W; X = Br, I) to form robust inclusion supramolecular complexes [{M₆X₈}Cl₆@2γ-CD]^2-. Single-crystal X-ray diffraction analyses revealed two conformational organizations within the adduct depending on the nature of the inner halide X within the {M₆X₈} core. Using ³⁵Cl NMR and UV-vis as complementary techniques, the kinetics of the hydrolysis process were shown to increase with the following order: {W₆I₈} < {W₆Br₈} ≈ {Mo₆I₈} < {Mo₆Br₈}. The complexation with γ-CD drastically enhances the hydrolytic stability of luminescent [{M₆X₈}Cl₆]^2- cluster-based units, which was quantitatively proved by the same techniques. The resulting host-guest complexation provides a protective shell against contact with water and offers promising horizons for octahedral clusters in biology as revealed by the low dark cytotoxicity and cellular uptake.