Organic radicals in a self-assembled grid

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Konstantin Shuvaev, Annie K. Powell and colleagues have designed a ligand containing the nitronyl nitroxide radical.  The ligand can self-assemble with copper(II) ions to give a [2 x 2] grid complex.

The nitronyl nitroxide radical coordinated via the oxo-atom of the N+-O- fragment in a chelating fashion and lies in the equatorial plane of the metal ion.

The nitronyl nitroxide radical coordinated via the oxo-atom of the N+-O- fragment in a chelating fashion and lies in the equatorial plane of the metal ion.

The high reactivity of organic radicals makes them difficult to use but the nitronyl nitroxide radical is one of the most stable and so can be used in the design of paramagnetic polytopic ligands as building blocks for supramolecular grids.  Most previous supramolecular grids have been made using diamagnetic ligands but the team found that being able to use a paramagnetic ligand resulted in a grid with interesting spin coupling and magnetic properties.

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A self-assembled Cu(II)4 [2 × 2] grid with organic radicals
Konstantin V. Shuvaev, Stephen Sproules, J. Mikko. Rautiainen, Eric J. L. McInnes, David Collison, Christopher E. Anson and Annie K. Powell
Dalton Trans., 2012
DOI: 10.1039/C2DT31946B, Paper

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