Lanthanide rhenium oxide single crystals from hydrothermal fluids: Synthesis and Structures of Ln2ReO5 (Ln = Pr, Nd), Ln3ReO7 (Ln = Gd and Tb) and Ln6ReO12 (Ln = Yb, Lu)

Lanthanide rhenium oxide single crystals from hydrothermal fluids: Synthesis and Structures of Ln2ReO5 (Ln = Pr, Nd), Ln3ReO7 (Ln = Gd and Tb) and Ln6ReO12 (Ln = Yb, Lu)
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热液中的镧系氧化铼单晶:Ln2ReO5 (Ln = Pr, Nd)、Ln3ReO7 (Ln = Gd 和 Tb) 和 Ln6ReO12 (Ln = Yb, Lu) 的合成和结构

DOI:
10.1016/j.jssc.2021.122779
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发表时间:
2022
影响因子:
3.3
通讯作者:
Kolis, Joseph W.
Kolis, Joseph W.
中科院分区:
化学3区
文献类型:
--
作者:
Kolambage, Mudithangani T.K.;Wetzel, George;Koehler, Kelliann;McMillen, Colin D.;Kolis, Joseph W.

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在高温水热条件下(650 °C/200 MPa),考察了稀土氧化物与ReO 2反应的相空间,重点考察了稀土氧化物与ReO 2的过量(3:1)或等摩尔比的反应。产物通常以高质量单晶分离,并通过单晶X射线衍射进行表征,在许多情况下为首次。镧系元素离子尺寸的系统变化对最终产物分布有显著影响,并且获得了宽范围的材料。特别是,合成的theLn 2 ReO 5系列的新成员的基础上更大的镧系元素Pr和Nd,使结构转变点之间的结构类型具有重叠和交错Re 2 O 8二聚体与Re-Re三键被精确定位。在中等尺寸的镧系元素中,获得了一种新的单斜晶型的Ln_3Re_O_7(Ln = Gd,Tb),其特征在于在共享边缘的稀土氧化物链中具有交替的长和短Re-Re键。在最小的镧系元素,theLn 6 ReO 12组成的特点是Yb和Lu。观察到各种不同的氧化态,这些都支持XPS表征。
The phase space involving reactions of rare earth oxides and ReO2was examined under high temperature hydrothermal conditions (650 ​°C/200 ​MPa), focusing on reactions containing either excess (3:1) or equimolar ratios of lanthanide oxides to ReO2. The products were generally isolated as high quality single crystals and characterized by single crystal X-ray diffraction, in many cases for the first time. The systematic variation of the size of the lanthanide ions had a significant effect on the final product distribution, and a wide range of materials was obtained. In particular, the synthesis of new members of theLn2ReO5series based on the larger lanthanides Pr and Nd enabled the structural transition point to be pinpointed between structure types having eclipsed and staggered Re2O8dimers with a Re–Re triple bond. In the moderately sized lanthanides, a new monoclinic polymorph ofLn3ReO7(Ln ​= ​Gd, Tb) was obtained, featuring alternating long and short Re–Re bonds in edge-sharing rhenium oxide chains. Among the smallest lanthanides, theLn6ReO12composition was characterized for Yb and Lu. A variety of rhenium oxidation states were observed and these were supported by XPS characterization.
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