Concise Chemistry Modulation of the SMM Behavior within a Family of Mononuclear Dy(III) Complexes
Concise Chemistry Modulation of the SMM Behavior within a Family of Mononuclear Dy(III) Complexes
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单核 Dy(III) 配合物家族中 SMM 行为的简明化学调节
DOI：
10.1021/acs.inorgchem.8b02602
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发表时间：
2018-12-03
影响因子：
4.6
通讯作者：
Pardo, Emilio
中科院分区：
文献类型：
--
作者：
Liu, Xiangyu;Ma, Xiufang;Pardo, Emilio
通过简单的化学反应、结构组装和转化，合成了四种Dy（Ⅲ）单核配合物：Dy（bpad）（3）中心点CH_3OH中心点H_2O（1），Dy（bpad）（2）（H_2O）（2）。NO3（2），[Dy（bpad）（2）（tmhd）]（3）和[Dy（bpad）（2）（btfa）]（4）（Hbpad = N-3-苯甲酰基吡啶-2-甲酰胺腙，tmhd = 2，2，6，6-四甲基庚烷-3，5-二酮，btfa = 3-苯甲酰基-1，1，1-三氟丙酮），具有不同的结构和局部对称性.这些配合物中Dy（III）离子周围的配位几何形状的差异影响晶体场的强度和每个Dy位点的局部各向异性张量（D）及其相对取向，因此引起不同的SIM行为，其具有106.93 K（1）、52.55 K（2）、48.16 K（3）、41.41K，4。用从头算方法解释了四种配合物的磁性和磁各向异性的差异，与实验结果相符合。
By means of the facile chemistry, structural assembly, and transformation of four mononuclear Dy(III) complexes, Dy(bpad)(3)center dot CH3OH center dot H2O (1), Dy(bpad)(2)(H2O)(2). NO3 (2), [Dy(bpad)(2)(tmhd)] (3), and [Dy(bpad)(2)(btfa)] (4) (Hbpad = N-3-benzoylpyridine-2-carboxamidrazone, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, btfa = 3-benzoyl-1,1,1-trifluoroacetone), with distinct architectures and local symmetries were established. The disparity of the coordination geometries around the Dy(III) ion among these complexes impacts the strength of the crystal field and the local tensor of anisotropy (D) of each Dy site and their relative orientations, therefore giving rise to diverse SIM behaviors with distinguishing relaxation energy barriers of 106.93 K for 1, 52.55 K for 2, 48.16 K for 3, and 51.41 K for 4. The differences of the magnetic property and the magnetic anisotropy for four complexes have been explained by ab initio calculations, which are corresponding to the experimental results.