Han Mei-Rong, Zhang Han-Tao, Wang Jia-Nan, Feng Si-Si, Lu Li-Ping
Institute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Shanxi University Taiyuan Shanxi 030006 P. R. China
Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University Taiyuan Shanxi 030006 P. R. China.
RSC Adv. 2019 Oct 10;9(55):32288-32295. doi: 10.1039/c9ra06920h. eCollection 2019 Oct 7.
Since Ln-CPs have excellent optical properties (higher color purity, longer fluorescence lifetime and higher quantum yield) and magnetic properties, it is of great significance to prepare dual magneto-optical materials based on Ln(iii). Herein, we obtained three versatile Ln-CPs, [Ln(HDTTA)(CHOH)] , derived from reactions of lanthanide salts (Ln = Tb 1, Dy 2, Ho 3) and a chiral and flexible ligand, namely, (+)-di--toluoyl-d-tartaric acid (d-HDTTA) in a methanol-water solution, at room temperature and pressure. The structures of these compounds have been characterized by single crystal and powder X-ray diffraction, infrared spectroscopy, elemental analyses and thermogravimetric analyses. Complexes 1-3 are isomorphic, crystallizing in the chiral trigonal 3 space group with the linkage of Ln ions and featuring 1D propeller chain structures. The circular dichroism spectra confirm that the complexes maintain the chirality from the ligands. Furthermore, the luminescent and magnetic properties have been investigated, relying on intrinsic properties of the lanthanide ions. The photoluminescence measurements indicate that 1, 2 and 3 show strong green, white and blue emission bands with CIE chromaticity coordinates of (0.32, 0.56), (0.29, 0.26) and (0.21, 0.12), respectively. The decay lifetime curve of 1 shows the exponential decay with long lifetime of 1.169 ms and the relative quantum yield for 1 was 19.31%. In addition, the magnetic properties of complexes 1-3 have been investigated by measuring the magnetic susceptibility in the temperature range of 2-300 K. They are all dominated by spin-orbit coupling and ligand field perturbation, and the exchange coupling between Ln ions is almost negligible. Therefore, complexes 1-3 are promising chiral, optical and magnetic multifunctional materials.
由于镧系元素配合物（Ln-CPs）具有优异的光学性质（更高的色纯度、更长的荧光寿命和更高的量子产率）和磁性，制备基于Ln(III)的双磁光材料具有重要意义。在此，我们通过镧系盐（Ln = Tb 1、Dy 2、Ho 3）与一种手性且灵活的配体，即(+)-二-对甲苯酰基-d-酒石酸（d-HDTTA）在甲醇-水溶液中于室温和常压下反应，得到了三种通用的Ln-CPs，[Ln(HDTTA)(CHOH)] 。这些化合物的结构已通过单晶和粉末X射线衍射、红外光谱、元素分析和热重分析进行了表征。配合物1-3是同构的，在手性三角3空间群中结晶，具有Ln离子的连接，呈现出一维螺旋链结构。圆二色光谱证实配合物保留了配体的手性。此外，基于镧系离子的固有性质对其发光和磁性进行了研究。光致发光测量表明，1、2和3分别显示出强的绿色、白色和蓝色发射带，CIE色度坐标分别为(0.32, 0.56)、(0.29, 0.26)和(0.21, 0.12)。1的衰减寿命曲线显示出指数衰减，长寿命为1.169 ms，1的相对量子产率为19.31%。此外，通过在2-300 K温度范围内测量磁化率对配合物1-3的磁性进行了研究。它们都受自旋-轨道耦合和配体场微扰支配，Ln离子之间的交换耦合几乎可以忽略不计。因此，配合物1-3是有前途的手性、光学和磁性多功能材料。
