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基于手性酒石酸衍生物和铕的发光与磁性双功能配位络合物。

Luminescent and magnetic bifunctional coordination complex based on a chiral tartaric acid derivative and europium.

作者信息

Han Mei Rong, Li Shao Dong, Ma Ling, Yao Bang, Feng Si Si, Zhu Miao Li

机构信息

Institute of Molecular Science, Key Laboratory of Chemical Biology and Molecular Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China.

Department of Chemistry, Changzhi University, Changzhi 046011, People's Republic of China.

出版信息

Acta Crystallogr C Struct Chem. 2019 Sep 1;75(Pt 9):1220-1227. doi: 10.1107/S205322961901060X. Epub 2019 Aug 6.

DOI:10.1107/S205322961901060X
PMID:31484809
Abstract

A new mononuclear europium complex incorporating the (+)-di-p-toluoyl-D-tartaric acid (D-HDTTA) ligand, namely, catena-poly[tris{μ-3-carboxy-2,3-bis[(4-methylphenyl)carbonyloxy]propanoato}tris(methanol)europium(III)], [Eu(CHO)(CHOH)], (I), has been synthesized and characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and single-crystal X-ray diffraction analysis. The structure analysis indicates that complex (I) crystallizes in the trigonal space group R3 and exhibits an infinite one-dimensional chain structure, in which the Eu ion is surrounded by six O atoms from six D-HDTTA ligands and three O atoms from three coordinated methanol molecules, thus forming a tricapped trigonal prism geometry. The D-HDTTA ligand is partially deprotonated and adopts a μ-coordination mode via two carboxylate groups to link adjacent Eu ions, affording an infinite one-dimensional propeller-shaped coordination polymer chain along the c axis, with an Eu...Eu distance of 7.622 (1) Å. Moreover, C-H...π interactions lead to the formation of helical chains running along the c axis and the whole structure displays a snowflake pattern in the ab plane. The circular dichroism spectrum confirms the chirality of complex (I). The solid-state photoluminescence properties were also investigated at room temperature and (I) exhibits characteristic red emission bands derived from the Eu ion (CIE 0.63, 0.32), with a reasonably long lifetime of 0.394 ms, indicating effective energy transfer from the ligand to the metal centre. In addition, a magnetic investigation reveals single-ion magnetic behaviour. The spin-orbit coupling parameter (λ) between the ground and excited states is fitted to be 360 (2) cm through Zeeman perturbation. Therefore, complex (I) may be regarded as a chiral optical-magneto bifunctional material.

摘要

一种包含(+)-二对甲苯甲酰基-D-酒石酸(D-HDTTA)配体的新型单核铕配合物,即链状聚[三{μ-3-羧基-2,3-双[(4-甲基苯基)羰氧基]丙酸根}三(甲醇)铕(III)],[Eu(CHO)(CHOH)],(I),已通过红外光谱、元素分析、粉末X射线衍射和单晶X射线衍射分析进行了合成与表征。结构分析表明配合物(I)结晶于三方空间群R3,呈现出无限一维链状结构,其中铕离子被来自六个D-HDTTA配体的六个氧原子和来自三个配位甲醇分子的三个氧原子所包围,从而形成一个三帽三棱柱几何构型。D-HDTTA配体部分去质子化,并通过两个羧酸根基团采用μ-配位模式连接相邻的铕离子,沿c轴形成无限一维螺旋桨状配位聚合物链,铕...铕距离为7.622 (1) Å。此外,C-H...π相互作用导致沿c轴形成螺旋链,整个结构在ab平面呈现雪花图案。圆二色光谱证实了配合物(I)的手性。还在室温下研究了固态光致发光性质,(I)表现出源自铕离子的特征红色发射带(CIE 0.63, 0.32),具有0.394 ms的合理长寿命,表明从配体到金属中心的有效能量转移。此外,磁性研究揭示了单离子磁行为。通过塞曼微扰将基态和激发态之间的自旋轨道耦合参数(λ)拟合为360 (2) cm。因此,配合物(I)可被视为一种手性光磁双功能材料。

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