1. Stable Heterometallic Cluster Ions based on Werner's Hexol
- Author
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Marsh, David A, Elliott, William S, Smith, Rachel M, Sharps, Meredith C, Baumeister, Mary K, Carnes, Matthew E, Zakharov, Lev N, Casey, William H, and Johnson, Darren W
- Subjects
Al-27 NMR spectroscopy ,aluminum clusters ,aqueous geochemistry ,heterometallic clusters ,polyoxocations ,27Al NMR spectroscopy ,Chemical Sciences ,Organic Chemistry - Abstract
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)2 Co(NH3 )4 ]3 (NO3 )6 (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)2 Co(NH3 )4 ]36+ 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 D2 O or [D6 ]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.
- Published
- 2017