首页> 外文期刊>International Journal of Quantum Chemistry >Influence of synthesis condition on product formation: hydrothermal auto-oxidated synthesis of five copper halides with ratio of Cu(I)/Cu(II) in 1:1, 2:1, 3:1, 4:1 and 1:0
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Influence of synthesis condition on product formation: hydrothermal auto-oxidated synthesis of five copper halides with ratio of Cu(I)/Cu(II) in 1:1, 2:1, 3:1, 4:1 and 1:0

机译:合成条件对产物形成的影响:Cu(I)/ Cu(II)比例为1:1、2:1、3:1、4:1和1:0的5种卤化铜的水热自氧化合成

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The hydrothermal synthesis and structural characterization of five copper iodides derived from chelated ligands, 1, 10-phenanthroline (phen), ethylenediamine (en) and 1, 3-propanediamine, are reported. Except monovalent copper compound 1 ((phen)Cu3I3 1), other four compounds ([Cu(phen)(2)I][CuI2] 2, [Cu(phen)(2)I][Cu3I4] 3, [Cu(en)(2)][Cu-4(phen)(2)I-6] 4 and [Cu(1, 3-propanediamine)(2)][CuI2](2) 5) are mixed-valent Cu(I)-Cu(II) compounds by partially auto-oxidated from Cu(I). Supramolecular frameworks of these compounds can be assembled by C/N-H center dot center dot center dot I hydrogen bonds, Cu(I)-Cu(II) interaction, weak Cu-I semicoordinate interaction, C-H center dot center dot center dot pi and pi-pi stacking interactions. It's noteworthy that we find hydrotheri-nal synthesis under higher pH value, higher synthesis temperature and longer reaction time can obtain higher ratio of Cu(I)/Cu(II) Copper iodides and organic ligand with lower steric hinderance is prone to coordinated with divalent copper to form cation unit. Finally, the fluorescent study shows 1 exhibits intense orange-red luminescence with long lifetime at 293 K and more intense emission and longer lifetime at 77 K. Moreover, the room temperature EPR spectra of above five compounds not only show the valence of copper but demonstrate the coordination environment of Cu(II) centre. (C) 2008 Elsevier Inc. All rights reserved.
机译:据报道,从螯合的配体1,10-菲咯啉(phen),乙二胺(en)和1,3-丙二胺中衍生出来的5种碘化铜的水热合成和结构表征。除一价铜化合物1((phen)Cu3I3 1)外,其他四种化合物([Cu(phen)(2)I] [CuI2] 2,[Cu(phen)(2)I] [Cu3I4] 3,[Cu( en)(2)] [Cu-4(phen)(2)I-6] 4和[Cu(1,3-丙二胺)(2)] [CuI2](2)5)是混合价的Cu(I )-Cu(II)化合物从Cu(I)部分自动氧化。这些化合物的超分子骨架可通过C / NH中心点中心点中心点I氢键,Cu(I)-Cu(II)相互作用,弱Cu-I半配位相互作用,CH中心点中心点中心点pi和pi组装-pi堆叠交互。值得注意的是,我们发现在较高的pH值,较高的合成温度和较长的反应时间下进行水热合成可以得到较高比例的碘化铜(I)/铜(II)和低位阻的有机配体容易与二价配位。铜形成阳离子单元。最终,荧光研究表明1表现出强烈的橙红色发光,在293 K处具有较长的寿命,在77 K处具有更强的发射和更长的寿命。此外,以上五种化合物的室温EPR谱不仅显示出铜的价,而且证明了Cu(II)中心的协调环境。 (C)2008 Elsevier Inc.保留所有权利。

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