Weng Guo-Guo, Huang Xin-Da, Hu Rui, Bao Song-Song, Zou Qian, Wen Ge-Hua, Zhang Yi-Quan, Zheng Li-Min
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.
Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University, Nanjing, 210023, P. R. China.
Chem Asian J. 2021 Sep 20;16(18):2648-2658. doi: 10.1002/asia.202100670. Epub 2021 Aug 3.
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) ⋅ CH COOH ⋅ 2H O (S-1, R-1), S-, R-Dy(cyampH) ⋅ 3H O (S-2, R-2), S-, R-Dy(cyampH) (C H COO) ⋅ 3H O (S-3, R-3) and S-, R-Dy(cyampH) ⋅ 0.5C H COOH ⋅ 2H O (S-4, R-4) [cyampH =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.
可控合成具有固有物理功能的均匀分布的配位聚合物纳米线是非常理想的，但具有挑战性。特别是，将手性和磁性结合到纳米线中在多功能材料和自旋电子器件中具有潜在应用。在此，我们报道了四对对映体纯的配位聚合物，其化学式为S-、R-Dy(cyampH) ⋅ CH₃COOH ⋅ 2H₂O (S-1、R-1)，S-、R-Dy(cyampH) ⋅ 3H₂O (S-2、R-2)，S-、R-Dy(cyampH) (C₂H₅COO) ⋅ 3H₂O (S-3、R-3) 和S-、R-Dy(cyampH) ⋅ 0.5C₂H₅COOH ⋅ 2H₂O (S-4、R-4) [cyampH = S-、R-(1-环己基乙基)氨基甲基膦酸]，它们是根据反应混合物的pH值和用作pH调节剂的特定羧酸获得的。有趣的是，化合物3以超长纳米线的形式获得，显示出包含膦酸根和丙酸根阴离子配体的一维中性链结构。而化合物1、2和4分别呈现为块状晶体、超螺旋和纳米棒，并表现出仅包含膦酸根配体的类似中性链结构。观察到化合物S-1和S-3具有单分子磁体 (SMM) 行为的缓慢磁化弛豫特性。进行了理论计算以合理化磁结构关系。
