Ligand Induced Double-Chair Conformation Ln(12) Nanoclusters Showing Multifunctional Magnetic and Proton Conductive Properties

Many methods have been utilized to adjust the size of superatomic metal nanoclusters, while tuning the geometric conformations of specific nanoclusters is rare. Here, we demonstrate that conformation variation can be realized by slightly modifying the ligand under maintaining the nuclei number of metal atoms. A series of novel "double-chair" conformation Ln(12) (Ln = Sm (1), Eu (2), Gd (3), Tb (4), and Dy (5)) clusters were generated by replacing 3-formylsalicylic acid with 2,3-dihydroxybenzoic acid in the L-12 nanocluster. Intriguingly, Dy-12 displays slow magnetic relaxation at low temperatures, while Gd-12 shows a large magnetocaloric effect (NICE) of 35.63 J kg(-1) K-1 at 2 K for Delta H = 7 T. Additionally, the introduction of numerous coordination water molecules in these clusters enables Dy-12 and Gd-12 with high proton conductivity, namely, 2.13 x 10(-4) and 3.62 x 10(-4) S cm(-1) under 358 K and 95% RH humidity conditions.