Affiliation:
1. Magnetism Key Laboratory of Zhejiang Province College of Materials and Chemistry China Jiliang University Hangzhou 310018 P. R. China
2. State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210023 P. R. China
3. Nantong Customs Comprehensive Technology Center Nantong 226006 P. R. China
Abstract
AbstractChiral lanthanide clusters have promising applications in chiral recognition, magneto‐optical memories, and spintronic devices. Nonetheless, the precise prediction and controlled development of homochiral polynuclear Ln‐complexes is still a challenge. Herein, through multidentate chelate synthetic strategy, a new homochiral hexagadolinium phosphonate cluster designated as R/S‐[Gd6(pmhpH)8(NO3)2(H2O)8]⋅19H2O (R/S‐1) was successfully obtained by reacting chiral phosphonomethylhomoproline(pmhpH3) with Gd(III) salt. The cluster, shaped like a lantern, is constructed from {GdO8} polyhedra and {PO3C} tetrahedra surrounded by eight pmhpH2− ligands. Within the structure, two types of gadolinium ions with different coordination modes are observed. Each Gd(III) ion is bound to two carboxylate oxygens and six phosphonate oxygens from the coordinated pmhpH2− ligands. Circular dichroism spectra comfirmed that R/S‐1 exists as a pair of enantiomers. Moreover, the cluster exhibits high thermal stability, decomposing at temperatures exceeding 335 °C. Notably, the chiral cluster materials can be used for enantiomeric recognition for tryptophan (Trp) with the differential pulse voltammetry (DPV) peak current ratio (ID/IL) 2.74. Besides, the magnetic measurements revealed that compound R‐1 exhibits a good magnetocaloric effect (MCE) with a maximum entropy change of −ΔSmmax=36.84 Jkg−1 K−1 at T=2 K and ΔH=7 T.
Funder
National Natural Science Foundation of China