Institut Lavoisier de Versailles, UMR 8180 CNRS, UVSQ, Université Paris-Saclay, 78035 Versailles, France.
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia.
Inorg Chem. 2022 Sep 12;61(36):14462-14469. doi: 10.1021/acs.inorgchem.2c02468. Epub 2022 Aug 30.
γ-Cyclodextrin (γ-CD) interacts in aqueous solution with octahedral halide clusters Na[{MX}Cl] (M = Mo, W; X = Br, I) to form robust inclusion supramolecular complexes [{MX}Cl@2γ-CD]. Single-crystal X-ray diffraction analyses revealed two conformational organizations within the adduct depending on the nature of the inner halide X within the {MX} core. Using Cl NMR and UV-vis as complementary techniques, the kinetics of the hydrolysis process were shown to increase with the following order: {WI} < {WBr} ≈ {MoI} < {MoBr}. The complexation with γ-CD drastically enhances the hydrolytic stability of luminescent [{MX}Cl] 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.
γ-环糊精（γ-CD）在水溶液中与八面体卤化物簇 Na[{MX}Cl]（M = Mo、W；X = Br、I）相互作用，形成稳定的包合超分子复合物[{MX}Cl@2γ-CD]。单晶 X 射线衍射分析表明，根据{MX}核内内卤化物 X 的性质，加成物内存在两种构象组织。使用 Cl NMR 和 UV-vis 作为补充技术，水解过程的动力学被证明按以下顺序增加：{WI} < {WBr} ≈ {MoI} < {MoBr}。γ-CD 的络合极大地提高了基于[{MX}Cl]簇的发光单元的水解稳定性，这同样通过上述技术得到了定量证明。所得主客体络合为与水接触提供了一个保护壳，并为八面体簇在生物学中的应用提供了广阔的前景，这一点从低暗毒性和细胞摄取率上得到了证明。
