Homochiral Dysprosium Phosphonate Nanowires: Morphology Control and Magnetic Dynamics

Controllable synthesis of uniformly distributed nanowires of coordination polymers with inherent physical functions is highly desirable but challenging. In particular, the combination of chirality and magnetism into nanowires has potential applications in multifunctional materials and spintronic devices. Herein, we report four pairs of enantiopure coordination polymers with formulae S-, R-Dy(cyampH)₃  ⋅ CH₃ COOH ⋅ 2H₂ O (S-1, R-1), S-, R-Dy(cyampH)₃  ⋅ 3H₂ O (S-2, R-2), S-, R-Dy(cyampH)₂ (C₂ H₅ COO) ⋅ 3H₂ O (S-3, R-3) and S-, R-Dy(cyampH)₃  ⋅ 0.5C₂ H₅ COOH ⋅ 2H₂ O (S-4, R-4) [cyampH₂ =S-, R-(1-cyclohexylethyl)aminomethylphosphonic acids], which were obtained depending on the pH of the reaction mixtures and the specific carboxylic acid used as pH regulator. Interestingly, compounds 3 were obtained as superlong nanowires, showing 1D neutral chain structure which contains both phosphonate and propionate anion ligands. While compounds 1, 2 and 4 appeared as block-like crystals, superhelices and nanorods, respectively, and exhibited similar neutral chain structures containing only phosphonate ligand. Slow magnetization relaxation characteristic of single-molecule magnet (SMM) behavior was observed for compounds S-1 and S-3. Theoretical calculations were performed to rationalize the magneto-structural relationships.