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由双三齿配体2,3,5,6-四(2-吡啶基)吡嗪桥联的镧系元素硝酸根配合物:合成、晶体结构、 Hirshfeld表面分析、发光性质、密度泛函理论计算及磁行为

Lanthanide nitrato complexes bridged by the bis-tridentate ligand 2,3,5,6-tetra(2-pyridyl)pyrazine: Syntheses, crystal structures, Hirshfeld surface analyses, luminescence properties, DFT calculations, and magnetic behavior.

作者信息

Cai Li-Ling, Zhang Sheng-Mei, Li Yan, Wang Kai, Li Xue-Ming, Muller Gilles, Liang Fu-Pei, Hu Ya-Tao, Wang Gui-Xia

机构信息

Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, PR China.

Department of Chemistry, San José State University, One Washington Square, San José, CA, 95192-0101, USA.

出版信息

J Lumin. 2021 Apr;232. doi: 10.1016/j.jlumin.2020.117835. Epub 2020 Dec 15.

Abstract

Six dinuclear lanthanide(III) nitrato complexes Ln(NO)(HO) (where tppz = 2,3,5,6-tetra(2-pyridyl) pyrazine and Ln(III) = Nd (), Sm (), Eu (), Gd (), Tb (), and Dy ()) with bis-tridentate N-heterocyclic 2,3,5,6-tetra(2-pyridyl)pyrazine as bridging ligand have been solvothermally synthesized and characterized via elemental analysis, infrared spectroscopy, thermogravimetric analysis, single-crystal X-ray diffraction, and powder X-ray diffraction. The 3-D Hirshfeld surface and 2-D fingerprint plots show that the main interactions in - are the O⋯H/H⋯O intermolecular interactions with relative contributions of about 62%. Although the poor lanthanide(III)-centered luminescence properties clearly point to the efficiency of nonradiative quenching processes (presence of water molecules in the coordination sphere of the lanthanide(III) ions), the ligand tppz is better suited to sensitize the lanthanide(III)'s emissions of Eu and Nd than Sm, Tb, and Dy. Finally, the magnetic data of Dy comple× reveals antiferromagnetic coupling between Dy ions.

摘要

六种双核镧系(III)硝酸根配合物Ln(NO)(HO)(其中tppz = 2,3,5,6 - 四(2 - 吡啶基)吡嗪,Ln(III) = Nd ()、Sm ()、Eu ()、Gd ()、Tb ()和Dy ()),以双三齿N - 杂环2,3,5,6 - 四(2 - 吡啶基)吡嗪作为桥联配体,通过溶剂热法合成,并通过元素分析、红外光谱、热重分析、单晶X射线衍射和粉末X射线衍射进行了表征。三维Hirshfeld表面和二维指纹图谱表明,-中的主要相互作用是O⋯H/H⋯O分子间相互作用,相对贡献约为62%。尽管以镧系(III)为中心的发光性能较差,这清楚地表明了非辐射猝灭过程的效率(镧系(III)离子配位球中存在水分子),但配体tppz比Sm、Tb和Dy更适合敏化Eu和Nd的镧系(III)发射。最后,Dy配合物的磁性数据揭示了Dy离子之间的反铁磁耦合。

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