Department of Chemistry & Biochemistry and Materials Science Institute, University of Oregon, Eugene, OR, 97403-1253, USA.
CAMCOR, University of Oregon, 1443 East 13th Ave., Eugene, OR, 97403, USA.
Angew Chem Int Ed Engl. 2017 Jul 17;56(30):8776-8779. doi: 10.1002/anie.201704073. Epub 2017 Jun 19.
Large aqueous ions are interesting because they are useful in materials science (for example to generate thin films) but also because they serve as molecular models for the oxide-aqueous mineral interface where spectroscopy is difficult. Here we show that new clusters of the type M[(μ-OH) Co(NH ) ] (NO ) (M=Al, Ga) can be synthesized using Werner's century-old cluster as a substitutable framework. We substituted Group 13 metals into the hexol Co[(μ-OH) Co(NH ) ] ion to make diamagnetic heterometallic ions. The solid-state structure of the hexol-type derivatives were determined by single-crystal XRD and NMR spectroscopy and confirmed that the solid-state structure persists in solution after dissolution into either D O or [D ]DMSO. Other compositions besides these diamagnetic ions can undoubtedly be made using a similar approach, which considerably expands the number of stable aqueous heteronuclear ions.
大的水合离子很有趣，因为它们在材料科学中有应用（例如，用于生成薄膜），而且它们还可以作为光谱学难以研究的氧化物-水矿物界面的分子模型。在这里，我们展示了可以使用 Werner 一个世纪前的团簇作为可替代的骨架来合成新型 M(μ-OH)Co(NH3)6类型的簇（M=Al、Ga）。我们将第 13 族金属取代到六羟合 Co[(μ-OH)Co(NH3)6]离子中，制得抗磁性异金属离子。通过单晶 XRD 和 NMR 光谱确定了六羟合型衍生物的固态结构，并证实其在溶解于 D2O 或 [D6]DMSO 后，在溶液中的固态结构仍然存在。无疑可以使用类似的方法制备除这些抗磁性离子以外的其他组成，这大大增加了稳定的水合异核离子的数量。
