Identification of Yb and Ce complexes containing 2,2,6,6-tetramethyl-heptane-2,4-dionate ligand: Syntheses, structures and calculations

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2025-02-01 Epub Date: 2024-11-26 DOI:10.1016/j.poly.2024.117317

Guan Peng , Wei Xu , Fangfang Chen

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Abstract

In this work, in order to identify the structures of Yb-TMHD (TMHD = 2,2,6,6-tetramethyl-heptane-2,4-dionate) and Ce-TMHD in commercialized products which are usually used as the precursors of Yb/Ce-codoped silica fiber preforms, Yb(TMHD)₃ (Ⅰ), Yb(TMHD)₃(H₂O) (Ⅱ), and Ce(TMHD)₄ (Ⅲ) were synthesized. And their structures were systematically characterized by elemental analysis, nuclear magnetic resonance (NMR), Infrared spectrometry (IR), X-ray single crystal diffraction and thermogravimetric analysis (TGA). The crystal structure of a new complex Yb(TMHD)₃(H₂O) (Ⅱ) was confirmed: triclinic and space group P-1, a = 12.5017(5) Å, b = 13.9289(6) Å, c = 14.5519(6) Å, V = 1890.48(15) Å³. It is verified that Ce(TMHD)₄ is the structure of Ce-doped organic source rather than Ce(TMHD)₃ from different synthesis methods, while Yb(TMHD)₃ can be the stable structure as Yb organic source. The quantum chemical calculation also confirmed the better thermodynamic stability of Yb(TMHD)₃ than that of Yb(TMHD)₃(H₂O). The IRI calculation results verify the coordination mode and indicate that the formation of crystals is related to the interaction between ligand molecules.

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含2,2,6,6-四甲基庚烷-2,4-二酸配体的Yb和Ce配合物的鉴定：合成、结构和计算

为了鉴定Yb-TMHD （TMHD = 2,2,6,6-四甲基庚烷-2,4-二酸酯）和Ce-TMHD的结构，本文合成了Yb(TMHD)3（Ⅰ）、Yb(TMHD)3(H2O)（Ⅱ）和Ce(TMHD)4（Ⅲ）。并用元素分析、核磁共振（NMR）、红外光谱（IR）、x射线单晶衍射和热重分析（TGA）对其结构进行了系统表征。确定了新的配合物Yb(TMHD)3(H2O)（Ⅱ）的晶体结构为三斜和空间群P-1， a = 12.5017(5) Å， b = 13.9289(6) Å， c = 14.5519(6) Å， V = 1890.48（15） Å3。通过不同的合成方法验证了Ce(TMHD)4是Ce掺杂有机源的结构，而不是Ce(TMHD)3，而Yb(TMHD)3可以作为Yb有机源的稳定结构。量子化学计算也证实了Yb(TMHD)3的热力学稳定性优于Yb(TMHD)3（H2O）。IRI计算结果验证了配位模式，表明晶体的形成与配体分子之间的相互作用有关。

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产品信息

麦克林

Ce(NH4)2(NO3)6

麦克林

Ce(NO3)3·6H2O

麦克林

sodium hydroxide

来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.