一锅法钆双核配合物:结构与磁性能

Fu-Wei Zheng, Lin Hua, Zhi-Yong He, Feng Geng, Yan Li, Long Wang, Xiang-Jun Zhu, Guo-Fang Li, Xian-Ying Duan, Hui-Qing Zhang, Hai-Tao Chen
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摘要

通过使用 2-羟基苯甲醛或 2-羟基-1-萘甲醛、2-氨基苯酚、吡啶-2-基甲胺和 Gd(NO3)3-6H2O 在 CH3CN 中(H2L1 = (E)-2-((2- 羟基苯亚甲基)氨基),得到了两个蝴蝶状双核钆(III)(Gd)配合物 [Gd2(L1)2(H2L3)2(NO3)2] (1)和 [Gd2(L2)2(H2L3)2(NO3)2] (2)、H2L1=(E)-2-((2-羟基苯亚甲基)氨基)苯酚,H2L2=(E)-1-(((2-羟基苯基)亚氨基)甲基)萘-2-醇,H2L3=吡啶-2-基甲胺)。结构分析表明,所有配体作为保护单元都能在外围保护中心的钆(III)离子。磁化研究显示,络合物 1 在 4 K(ΔH = 7 T)条件下的磁致效应为 14.45 J-kg-1-K-1,络合物 2 在 2 K(ΔH = 7 T)条件下的磁致效应为 12.69 J-kg-1-K-1。在复合物 1 和 2 中,虽然配位构型相同,但 MCE 的显著差异可能是由于外围配体的调整导致了配位场强度的变化。配体的电子亲和力会影响配体与钆(III)离子之间的相互作用。
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Binuclear Gadolinium Complex by One‐Pot Method: Structure and Magnetic Property
Two butterfly‐like binuclear Gadolinium(III) (Gd) complex [Gd2(L1)2(H2L3)2(NO3)2] (1) and [Gd2(L2)2(H2L3)2(NO3)2] (2) were obtained by using 2‐hydroxybenzaldehyde or 2‐hydroxy‐1‐naphthaldehyde, 2‐aminophenol, pyridin‐2‐ylmethanamine and Gd(NO3)3·6H2O in CH3CN (H2L1 = (E)‐2‐((2‐hydroxybenzylidene)amino)phenol, H2L2 = (E)‐1‐(((2‐hydroxyphenyl)imino)methyl)naphthalen‐2‐ol, H2L3 = pyridin‐2‐ylmethanamine). Structural analysis suggests that all the ligands as protective units protect the central Gd(III) ions at the periphery. Magnetization studies exhibited magnetocaloric effect of 14.45 J·kg−1·K−1 at 4 K under ΔH = 7 T for complex 1 and 12.69 J·kg−1·K−1 at 2 K under ΔH = 7 T for complex 2. In complexes 1 and 2, although the coordination configurations are the same, the significant difference in MCE may be due to the adjustments of the peripheral ligands leading to changes in the coordination field strength. The electron affinity of the ligands can impact the interaction between the ligands and Gd(III) ions.
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