Synthesis and structural characterization of an air and water stable divalent Europium squarate prepared by in situ reduction
Synthesis and structural characterization of an air and water stable divalent Europium squarate prepared by in situ reduction
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DOI：
10.1016/j.jssc.2021.122048
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发表时间：
2021-05
影响因子：
3.3
通讯作者：
Jason P. Stone;Elizabeth A. Decoteau;M. Polinski
中科院分区：
文献类型：
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作者：
Jason P. Stone;Elizabeth A. Decoteau;M. Polinski
合成了一种新的空气和水稳定的二价Eu(C4O4)(H2O)[Eu(C4O4)(H2O)](1)。用锌汞齐和温和的溶剂热加热，通过原位还原三价铕盐合成了1。得到的二价铕金属中心在空气和水中都是稳定的。这表明这种方法不需要严格的厌氧条件。通过改变合成条件，合成了两个新的三价稀土方酸盐[Ln2(C4O4)2(C4O3OH)2(H2O)12](Ln=La-ND)(2)和[Ln2(C4O4)3(H2O)8](Ln=Dy-Lu)(3)。单晶X射线衍射分析表明，1在C2/m空间群中结晶，是由具有不寻常的三角十二面体(CN=8)几何构型的EuO7(H2O)多面体片状构成的三维结构；2在P 1‘空间群中结晶，是由LNO3(H2O)6单层正方形反棱柱(CN=9)金属中心构成的0D结构；3在P21/n空间群中结晶，是由LNO4(H2O)4方形反棱柱(CN=8)金属中心构成的2D片状结构。在所有的结构中，四方配体以不同的，有时是不常见的配位方式和配位能力与金属中心结合。本文介绍了化合物1、2和3的合成、结构和固态UV-Vis-NIR光谱。
A new air and water stable divalent Europium squarate,[Eu (C 4 O 4)(H 2 O)](1), has been prepared and structurally characterized. 1 was synthesized by in situ reduction of a trivalent Europium salt using a Zinc amalgam and mild solvothermal heating. The resulting divalent Europium metal centers in 1 are both air and water stable. This demonstrates that this methodology does not require strict anaerobic conditions. A variation on the synthetic conditions used to prepare 1 (sans the Zinc amalgam) yielded two new series of trivalent lanthanide squarates,[Ln 2 (C 4 O 4) 2 (C 4 O 3 OH) 2 (H 2 O) 12](Ln= La–Nd)(2) and [Ln 2 (C 4 O 4) 3 (H 2 O) 8](Ln= Dy–Lu)(3), which have also been structurally and spectroscopically characterized. Single crystal X-ray diffraction analysis reveals that 1 crystallizes in the C2/m space group and is a 3D structure constructed from sheets of EuO 7 (H 2 O) polyhedra with an unusual triangular dodecahedral (CN= 8) geometry, 2 crystallizes in the P 1¯ space group and is a 0D structure constructed from LnO 3 (H 2 O) 6 monocapped square antiprismatic (CN= 9) metal centers, and 3 crystallizes in the P2 1/n space group and is a 2D sheet structure constructed from LnO 4 (H 2 O) 4 square antiprismatic (CN= 8) metal centers. In all structures, the squarate ligands bind to the metal centers with varying, and sometimes uncommon, coordination modes and denticities. Herein, the synthesis, structure, and solid-state UV–vis–NIR spectroscopy of 1, 2, and 3 are presented.