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Stable Heterometallic Cluster Ions based on Werner's Hexol.

  • Author(s): Marsh, David A
  • Elliott, William S
  • Smith, Rachel M
  • Sharps, Meredith C
  • Baumeister, Mary K
  • Carnes, Matthew E
  • Zakharov, Lev N
  • Casey, William H
  • Johnson, Darren W
  • et al.
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.

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