三价镧系元素的2-巯基苯并噻唑配合物的发光性质

Luminescent properties of 2-mercaptobenzothiazolates of trivalent lanthanides.

作者信息

Ilichev Vasily A, Pushkarev Anatoly P, Rumyantcev Roman V, Yablonskiy Artem N, Balashova Tatyana V, Fukin Georgy K, Grishin Dmitry F, Andreev Boris A, Bochkarev Mikhail N

机构信息

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, Russian Federation.

出版信息

Phys Chem Chem Phys. 2015 Apr 28;17(16):11000-5. doi: 10.1039/c4cp05928j.

DOI:10.1039/c4cp05928j

PMID:25824367

Abstract

A series of lanthanide complexes (Ln = Nd, Sm, Eu, Gd and Yb) with anionic 2-mercaptobenothiazolate (mbt) ligands were synthesized. Depending on the solvents chosen for the synthesis, Ln(mbt)3(THF)2 and Ln(mbt)3(Et2O) complexes were precipitated from THF and Et2O solutions respectively. The structure of Yb(mbt)3(Et2O) was determined by X-ray analysis. Photophysical properties of the complexes were studied. It was found that under photoexcitation Nd and Yb derivatives exhibit bright metal-centered luminescence in the NIR region while Sm(mbt)3(THF)2 demonstrates intensive visible emission corresponding to (4)G5/2 → (6)HJ (J = 5/2, 7/2, 9/2, 11/2) f-f transitions of Sm(3+) along with NIR emission of moderate intensity. In the case of europium compounds as well as Sm(mbt)3(Et2O) no luminescence was detected. It is assumed that the difference in photoluminescence of Yb and Eu complexes can be explained by an intramolecular electron transfer process, which efficiently proceeds in these compounds.

摘要

合成了一系列带有阴离子2-巯基苯并噻唑（mbt）配体的镧系配合物（Ln = Nd、Sm、Eu、Gd和Yb）。根据合成所选用的溶剂，Ln(mbt)3(THF)2和Ln(mbt)3(Et2O)配合物分别从THF和Et2O溶液中沉淀出来。通过X射线分析确定了Yb(mbt)3(Et2O)的结构。研究了这些配合物的光物理性质。结果发现，在光激发下，Nd和Yb衍生物在近红外区域呈现出明亮的以金属为中心的发光，而Sm(mbt)3(THF)2则表现出强烈的可见光发射，对应于Sm(3+)的(4)G5/2 → (6)HJ（J = 5/2、7/2、9/2、11/2）f-f跃迁以及中等强度的近红外发射。对于铕化合物以及Sm(mbt)3(Et2O)，未检测到发光现象。据推测，Yb和Eu配合物光致发光的差异可以通过分子内电子转移过程来解释，该过程在这些化合物中有效地发生。