Os(VI)O<sub>2</sub>/K
Metal–Organic Frameworks:
Infinite Chain, Grid, and Porous Networks
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Abstract
The
design of multianionic chelating ligands as new organic linker
for producing metal–organic frameworks (MOFs) is discussed.
Three potentially polyanionic pro-ligands, 3,5-di-<i>tert</i>-butyl-2-hydroxy-<i>N</i>-(2-hydroxyethyl)benzamide (<sup>1</sup>LH<sub>3</sub>), bis(2-aminoethyl)-5-(<i>tert</i>-butyl)-2-hydroxyisophthalate (<sup>2a</sup>LH<sub>3</sub>), and
5-(<i>tert</i>-butyl)-2-hydroxy-<i>N</i>1,<i>N</i>3-bis(1-hydroxy-2-methylpropan-2-yl)isophthalamide (<sup>2b</sup>LH<sub>3</sub>), were synthesized and found to coordinate
the osmyl ion in trianionic NO<sub>2</sub> fashion through the N-amidate,
O-phenolate, and O-alcoholate donor atoms. The X-ray crystal structures
of three dioxo-Os(VI) complexes: [Os<sub>2</sub>O<sub>4</sub>(<sup>1</sup>L)<sub>2</sub>(OH)K<sub>2</sub>(H<sub>2</sub>O)(C<sub>3</sub>H<sub>6</sub>O)] (<b>Os</b><sup><b>1</b></sup>), [OsO<sub>2</sub>(<sup>2a</sup>L<sup>3–</sup>)(MeOH)<sub>4</sub>(MeO)K<sub>2</sub>] (<b>Os</b><sup><b>2a</b></sup>), and [OsO<sub>2</sub>(<sup>2b</sup>L)(H<sub>2</sub>O)(C<sub>3</sub>H<sub>6</sub>O)K] (<b>Os</b><sup><b>2b</b></sup>) reveal that the
osmyl moiety and the ligand establish distinctive interactions with
the potassium ions, yielding unprecedented infinite network from stepladder
chain (in <b>Os</b><sup><b>2b</b></sup>) and 2D-grid (in <b>Os</b><sup><b>1</b></sup>) to 3D-porous H-bonding network
(in <b>Os</b><sup><b>2a</b></sup>)
