Influence of the Coordination Environment on the EPR Spectra of Mononuclear Gd Thiocyanates

IF 1.1 3区化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Coordination Chemistry Pub Date : 2024-07-27 DOI:10.1134/S1070328423601413

S. P. Petrosyants, A. B. Ilyukhin, K. A. Babeshkin, E. A. Ugolkova, V. V. Minin, P. S. Koroteev, N. N. Efimov

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引用次数: 0

Abstract

Using the synthesized salt Gd(NCS)₃·6H₂O, previously unknown mononuclear molecular complexes [Gd(H₂O)(bpy)₂(NCS)₃]·0.5(bpy)·H₂O, [Gd(H₂O)(phen)₂(NCS)₃]·phen·0.5H₂O as well as ionic ones [Hbpy][Gd(NCS)₄(bpy)₂]·H₂O, [Hphen][Gd(NCS)₄(phen)₂] (bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline) were prepared. Structural characteristics of the obtained compounds were determined using X-ray diffraction data. The magnetic susceptibility and EPR data of the new Gd complexes are considered taking into account the features of their composition and structure. Due to the peculiarities of the electronic structure, Gd complexes can serve as test systems for analyzing the field strength of ligands and the geometry of the local environment of the 4f-metal ion. It is shown that EPR spectroscopy is highly efficient method for determining the spin Hamiltonian parameters and, consequently, for characterizing the local environment of the gadolinium ion in complexes. However, the EPR method does not allow one to determine the sign of the splitting parameter in the zero field D, which requires additional studies.

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配位环境对单核硫氰酸钆 EPR 光谱的影响

摘要利用合成盐 Gd(NCS)3-6H2O，以前未知的单核分子配合物 [Gd(H2O)(py)2(NCS)3]-0.5(py)-H2O、[Gd(H2O)(phen)2(NCS)3]-phen-0.5H2O 以及离子型化合物 [Hbpy][Gd(NCS)4(bpy)2]-H2O、[Hphen][Gd(NCS)4(phen)2]（bpy 为 2,2'-联吡啶，phen 为 1,10-菲罗啉）。利用 X 射线衍射数据确定了所获化合物的结构特征。考虑到新钆配合物的组成和结构特征，研究了它们的磁感应强度和 EPR 数据。由于电子结构的特殊性，钆配合物可以作为分析配体场强和 4f 金属离子局部环境几何形状的测试系统。研究表明，EPR 光谱法是确定自旋哈密顿参数的高效方法，因此也是确定钆配合物中钆离子局部环境特征的高效方法。不过，EPR 方法无法确定零场 D 中分裂参数的符号，这需要额外的研究。

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来源期刊

Russian Journal of Coordination Chemistry 化学-无机化学与核化学

CiteScore

2.40

自引率

15.80%

发文量

审稿时长

7.2 months

期刊介绍： Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.