Wen He-Rui, Hu Jun-Jie, Yang Kai, Zhang Jia-Li, Liu Sui-Jun, Liao Jin-Sheng, Liu Cai-Ming
School of Chemistry and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, People's Republic of China.
School of Chemistry and Chemical Engineering, Jinggangshan University, Ji'an 343000, People's Republic of China.
Inorg Chem. 2020 Mar 2;59(5):2811-2824. doi: 10.1021/acs.inorgchem.9b03164. Epub 2020 Feb 13.
A family of chiral 3d-4f heterometallic complexes, namely, ZnLn(,-L)(HO)) [Ln = Dy (), Tb ()], ZnLn(,-L)(HO) [Ln = Dy (), Tb ()], [ZnLn(,-L)(CO)(NO)]·2CHOH [Ln = Dy (), Tb ()], and [ZnLn(,-L)(CO)(NO)]·2CHOH [Ln = Dy (), Tb ()] {HL = cyclohexane-1,2-diylbis(azanediyl)bis(methylene)bis(2-methoxyphenol)}, has been synthesized and characterized. Crystal structure analysis reveals that complexes - are isostructural trinuclear clusters crystallized in chiral space group 22, and - are isostructural tetranuclear clusters crystallized in chiral space group 1. Interestingly, the adjacent [ZnLn] units within the tetranuclear cluster in - are bridged by two carbonate anions incorporation of CO from air. Magnetic measurements indicate that complexes and exhibit field-induced single-molecule magnet behavior with energy barriers () of 22.46 and 38.70 K (or 41.87 K), respectively. Complex displays typical SMM behavior with = 19.61 K under zero dc field, while for complex , no obvious out-of-phase signals are observed even under 2 kOe dc field, the absence of SMM behavior. The solid-state luminescence studies reveal that all complexes display the characteristic fluorescence emission of lanthanide ions. Furthermore, the Kurtz-Perry measurements reveal these complexes are potential nonlinear optical materials.
合成并表征了一系列手性3d-4f异金属配合物，即[ZnLn(μ₃-L)(H₂O)] (ClO₄)₂ [Ln = Dy (1), Tb (2)]、[ZnLn(μ₃-L)(H₂O)] (ClO₄)₂ [Ln = Dy (3), Tb (4)]、[ZnLn(μ₃-L)(CO₃)(NO₃)]·2CH₃OH [Ln = Dy (5), Tb (6)]和[ZnLn(μ₃-L)(CO₃)(NO₃)]·2CH₃OH [Ln = Dy (7), Tb (8)] {HL = 环己烷-1,2-二亚基双(氮杂二亚基)双(亚甲基)双(2-甲氧基苯酚)}。晶体结构分析表明，配合物1 - 4是同构的三核簇，在手性空间群P2₁2₁2₁中结晶，配合物5 - 8是同构的四核簇，在手性空间群P1中结晶。有趣的是，配合物5 - 8中四核簇内相邻的[ZnLn]单元由两个碳酸根阴离子桥连，这是由于空气中的CO₂掺入所致。磁性测量表明，配合物1和3分别表现出场诱导单分子磁体行为，能垒(∆)为22.46和38.70 K(或41.87 K)。配合物2在零直流场下表现出典型的单分子磁体行为，∆ = 19.61 K，而对于配合物4，即使在2 kOe直流场下也未观察到明显的异相信号，即不存在单分子磁体行为。固态发光研究表明，所有配合物都显示出镧系离子的特征荧光发射。此外，库尔茨-佩里测量表明这些配合物是潜在的非线性光学材料。
