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Cyanide-Bridged Fe-Co Polynuclear Clusters Based on Four-Coordinate Cobalt(II)
17
Citations
56
References
2020
Year
Treatment of CoCl<sub>2</sub>·6H<sub>2</sub>O and tris(pyrazolyl-1-yl)borate tricyanoiron(III) anions at 55 °C afforded a series of new Fe-Co polynuclear clusters: {Co<sub>2</sub>Cl<sub>2</sub>(DMF)<sub>4</sub>[(Tp<sup>4-Me</sup>)Fe(CN)<sub>3</sub>]<sub>2</sub>} (<b>1</b>; Tp<sup>4-Me</sup> = hydridotris(4-methylpyrazol-1-yl)borate), (H<sub>3</sub>O<sup>+</sup>)@{Co<sub>4</sub>Cl<sub>4</sub>[(Tp<sup>4-Me</sup>)Fe(CN)<sub>3</sub>]<sub>4</sub>} (<b>2</b>), (MePh<sub>3</sub>P)<sub>4</sub>{Co<sub>6</sub>Cl<sub>6</sub>[(Tp<sup>4-Me</sup>)Fe(CN)<sub>3</sub>]<sub>6</sub>}·15CH<sub>3</sub>CN·3CH<sub>3</sub>OH·2H<sub>2</sub>O (<b>3</b>), and (BnEt<sub>3</sub>N)<sub>4</sub>{Co<sub>5</sub>Cl<sub>8</sub>[(Tp*)Fe(CN)<sub>3</sub>]<sub>4</sub>}·4CH<sub>3</sub>CN·2H<sub>2</sub>O (<b>4</b>; Tp*= hydridotris(3,5-dimethylpyrazol-1-yl)borate). They feature an asymmetric [Fe<sub>2</sub>Co<sub>2</sub>(CN)<sub>4</sub>] square, a pseudocubic [Fe<sub>4</sub>Co<sub>4</sub>(CN)<sub>12</sub>] cluster, a distorted-hexagonal-prism-shaped [Fe<sub>6</sub>Co<sub>6</sub>(CN)<sub>18</sub>] cage, and a bis(trigonal-bipyramidal) cluster of [Fe<sub>4</sub>Co<sub>5</sub>(CN)<sub>12</sub>] fused at one cobalt center, respectively. The Co(II) ions adopt a four-coordinate tetrahedral geometry except for half of <b>1</b> in an octahedral geometry. It should be mentioned that <b>3</b> and <b>4</b> provide two novel molecular skeletons in the cyanometalate family. Interestingly, <b>1</b> behaved as a single-molecule magnet with an effective energy barrier for spin reverse of 30.7 K at zero dc field. Our result demonstrated a possible self-assembly route toward high-nuclearity cyanide-bridged clusters by introducing four-coordinate cobalt(II) ions.
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