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Cl<sup>–</sup>-Templated Assembly of Novel Peanut-like Ln<sub>40</sub>Ni<sub>44</sub> Heterometallic Clusters Exhibiting a Large Magnetocaloric Effect
36
Citations
45
References
2019
Year
Two novel and fascinating high-nuclearity lanthanide-transition (4f-3d) heterometallic clusters were obtained based on an anion-template (Cl<sup>-</sup>) and ligand-controlled approach, formulated as [Gd<sub>40</sub>Ni<sub>44</sub>(CO<sub>3</sub>)<sub>12</sub>(CH<sub>3</sub>COO)<sub>4</sub>(IDA)<sub>44</sub>(C<sub>2</sub>O<sub>4</sub>)(μ<sub>2</sub>-O)<sub>4</sub>(μ<sub>3</sub>-OH)<sub>60</sub>(μ<sub>3</sub>-O)<sub>6</sub>(H<sub>2</sub>O)<sub>12</sub>]·Cl<sub>10</sub>·20H<sub>2</sub>O (abbreviated as Gd<sub>40</sub>Ni<sub>44</sub>, <b>1</b>) and [Eu<sub>40</sub>Ni<sub>44</sub>(CO<sub>3</sub>)<sub>12</sub>(CH<sub>3</sub>COO)<sub>6</sub>(IDA)<sub>44</sub>(C<sub>2</sub>O<sub>4</sub>)(μ<sub>2</sub>-O)<sub>4</sub>(μ<sub>3</sub>-OH)<sub>62</sub>(μ<sub>3</sub>-O)<sub>4</sub>(H<sub>2</sub>O)<sub>12</sub>]·Cl<sub>10</sub>·23H<sub>2</sub>O (abbreviated as Eu<sub>40</sub>Ni<sub>44</sub>, <b>2</b>), where H<sub>2</sub>IDA = iminodiacetic acid and H<sub>2</sub>C<sub>2</sub>O<sub>4</sub> = oxalic acid. Structural analysis exhibits that the compounds <b>1</b> and <b>2</b> were both constructed by two enticing bowl-like anion units Ln<sub>20</sub>Ni<sub>22</sub>, featuring peanut-like structures. Besides, the assembly of Ln<sub>20</sub>Ni<sub>22</sub> was templated by five Cl<sup>-</sup> ions. Magnetically, compound <b>1</b> shows a significant magnetocaloric effect, with -Δ<i>S</i><sub>m</sub> = 36.05 J kg<sup>-1</sup> K<sup>-1</sup> at 3 K for Δ<i>H</i> = 7 T.
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