具有单分子磁性的手性同核大环镝配合物

Zi-Hang Cheng, Ru-Chan Liu, Feng Gao
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摘要

一对对映体手性镝同核配合物:以大环手性配体(R,R,R,R-H2L/S,S,S,S-H2L)为基础,合成了一对对映体手性镝同核配合物:[(acac)4Dy2(R,R,R,R-L)](R-Dy)和[(acac)4Dy2(S,S,S,S-L)](S-Dy)(Hacac = 乙酰丙酮)、分别来自 4-叔丁基-2,6-二甲酰苯酚、乙酰丙酮镝和 (1R,2R)-/(1S,2S)-1,2-环己二胺的 [2+2] 模板缩合。圆二色光谱证实了它们的对映体手性。单晶结构显示,两个晶体学上独立的镝(III)离子具有不同 D4d 局部对称性的方形反斜面配位。此外,所选的 R-Dy 复合物具有铁磁性 Dy3+---Dy3+ 耦合的慢磁弛豫行为。
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Chiral Homodinuclear Dysprosium Macrocyclic Complexes with Single‐molecule Magnetic Behaviours
A pair of enantiomerically chiral dysprosium homodinuclear complexes: [(acac)4Dy2(R,R,R,R‐L)] (R‐Dy) and [(acac)4Dy2(S,S,S,S‐L)] (S‐Dy) (Hacac = acetylacetone) have been synthesized based on macrocyclic chiral ligands (R,R,R,R‐H2L/S,S,S,S‐H2L), derived from the [2+2] template condensation of 4‐tert‐butyl‐2,6‐diformylphenol, dysprosium acetylacetonate and (1R,2R)‐/(1S,2S)‐1,2‐cyclohexanediamine, respectively. Circular dichroism spectra confirms their enantiomeric chirality. Single‐crystal structures show two crystallographic independent dysprosium(III) ions have square antiprismatic coordination with different D4d local symmetry. Furthermore, the selected R‐Dy complex owns the slow magnetic relaxation behaviour with the ferromagnetic Dy3+···Dy3+ coupling.
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