Moushi, Eleni E. Lampropoulos, Christos Wernsdorfer, Wolfgang Nastopoulos, Vassilios Christou, George Tasiopoulos, Anastasios J. Inducing Single-Molecule Magnetism in a Family of Loop-of-Loops Aggregates: Heterometallic Mn<sub>40</sub>Na<sub>4</sub> Clusters and the Homometallic Mn<sub>44</sub> Analogue The syntheses, crystal structures, and magnetic properties of a new family of heterometallic Mn<sub>40</sub>Na<sub>4</sub> and homometallic Mn<sub>44</sub> loop-of-loops aggregates are reported. The reactions of [Mn<sub>3</sub>O(O<sub>2</sub>CMe)<sub>6</sub>(py)<sub>3</sub>]·py with 1,3-propanediol (pdH<sub>2</sub>) and 2-methyl-1,3-propanediol (mpdH<sub>2</sub>) in the presence of NaN<sub>3</sub> afforded [Mn<sub>10</sub>Na(μ<sub>3</sub>-O)<sub>2</sub>(O<sub>2</sub>CMe)<sub>13</sub>(pd)<sub>6</sub>(py)<sub>2</sub>]<sub>4</sub> (<b>1</b>)<sub>4</sub> and [Mn<sub>10</sub>Na(μ<sub>3</sub>-O)<sub>2</sub>(O<sub>2</sub>CMe)<sub>13</sub>(mpd)<sub>6</sub>(py)(H<sub>2</sub>O)]<sub>4</sub> (<b>2</b>)<sub>4</sub>, respectively. Mn<sub>40</sub>Na<sub>4</sub> complexes (<b>1</b>)<sub>4</sub> and (<b>2</b>)<sub>4</sub> consist of four Mn<sub>10</sub> loops linked through Na<sup>+</sup> ions to give a supramolecular aggregate with a saddle-like topology. Magnetic characterization of compound (<b>1</b>)<sub>4</sub> showed that each Mn<sub>10</sub> loop has an <i>S</i> = 4 ground-state spin and displays frequency-dependent in-phase and out-of-phase ac susceptibility signals. It also exhibits hysteresis loops that, however, are not typical of single-molecule magnets (SMMs) due to the existence of interloop interactions between the neighboring Mn<sub>10</sub> units of (<b>1</b>)<sub>4</sub> through the diamagnetic Na<sup>+</sup> ions, and also intermolecular interactions between different Mn<sub>40</sub>Na<sub>4</sub> aggregates. The magnetically discrete Mn<sub>44</sub> analogue was targeted with high priority and finally prepared from the reaction of [Mn<sub>3</sub>O(O<sub>2</sub>CMe)<sub>6</sub>(py)<sub>3</sub>]·py with pdH<sub>2</sub> in the presence of Mn(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O. The loop-of-loops structure of [Mn<sub>44</sub>(μ<sub>3</sub>-O)<sub>8</sub>(O<sub>2</sub>CMe)<sub>52</sub>(pd)<sub>24</sub>(py)<sub>8</sub>](ClO<sub>4</sub>)(OH)<sub>3</sub> (<b>3</b>) is essentially identical to those of (<b>1</b>)<sub>4</sub> and (<b>2</b>)<sub>4</sub>, with the most significant difference being that the four Na<sup>+</sup> ions of (<b>1</b>)<sub>4</sub> and (<b>2</b>)<sub>4</sub> have been replaced with Mn<sup>2+</sup> ions. Compound <b>3</b> is thus best described magnetically as a Mn<sub>44</sub> cluster. In accord with this description and the stronger exchange coupling between the four Mn<sub>10</sub> loops expected through the connecting Mn<sup>2+</sup> ions, magnetic susceptibility measurements revealed that <b>3</b> has an <i>S</i> = 6 ground-state spin and displays frequency-dependent in-phase and out-of-phase ac signals. Magnetization vs dc field sweeps on single-crystals of <b>3</b> displayed scan rate- and temperature-dependent hysteresis loops confirming that complex <b>3</b> is a new SMM, and is thus the second largest Mn cluster and SMM reported to date. Mn 44 cluster;Mn 44 analogue;heterometallic Mn 40Na;Mn 10 loop;Mn 3O;Magnetization vs dc field sweeps;Mn 10 units;Mn 40Na aggregates;Heterometallic Mn 40Na Clusters;SMM;Mn 10 loops;Homometallic Mn 44 AnalogueThe syntheses;exhibits hysteresis loops 2010-11-17
    https://acs.figshare.com/articles/dataset/Inducing_Single_Molecule_Magnetism_in_a_Family_of_Loop_of_Loops_Aggregates_Heterometallic_Mn_sub_40_sub_Na_sub_4_sub_Clusters_and_the_Homometallic_Mn_sub_44_sub_Analogue/2712538
10.1021/ja106666h.s003