Two Windmill-Shaped Ln<sub>18</sub> Nanoclusters Exhibiting High Magnetocaloric Effect and Luminescence
Qin Wang, Ya-Ting Yu, Ji‐Lei Wang, Jia-Nian Li, Ning-Fang Li, Xinrong Fan, Yan Xu
Abstract
The self-assembly of the high-nuclearity Ln-exclusive nanoclusters is challenging but of significance due to its aesthetically pleasing architectures and far-reaching latent applications in magnetic cooling technologies. Herein, two novel high-nuclearity lanthanide nanoclusters were successfully synthesized under solvothermal conditions, formulated as {[Gd 18 (IN) 20 (HCOO) 8 (μ 6 -O)(μ 3 -OH) 24 (H 2 O) 4 ]·4H 2 O} n and {[Eu 18 (IN) 16 (HCOO) 8 (CH 3 COO) 4 (μ 6 -O)(μ 3 -OH) 24 (H 2 O) 4 ]·5H 2 O} n (abbreviated as Gd 18 and Eu 18, HIN = isonicotinic acid). Both of them possess novel and exquisite windmill-shaped cationic cores in the family of high-nuclearity Ln-exclusive nanoclusters. Remarkably, the adjacent second building units are interconnected into a three-dimensional (3D) metal–organic framework by IN – ligands. As expected, the abundant existence of Gd III ions endows Gd 18 with a favorable magnetic entropy change at 2.0 K for Δ H = 7.0 T (−Δ S m max = 40.0 J kg –1 K –1 ), and Eu 18 displays the typical luminescence of Eu III ions.