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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.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704073
Subject(s) - heteronuclear molecule , aqueous solution , ion , cluster (spacecraft) , chemistry , dissolution , diamagnetism , spectroscopy , crystallography , nuclear magnetic resonance spectroscopy , inorganic chemistry , stereochemistry , physics , organic chemistry , quantum mechanics , computer science , magnetic field , programming language
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(NH 3 ) 4 ] 3 (NO 3 ) 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(NH 3 ) 4 ] 3 6+ 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 2 O or [D 6 ]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.