铜(3-氨基,5-甲基异恶唑)4 (ClO4)2和铜(3-氨基,5-甲基异恶唑)4 (NO3)2的EPR研究

B.A. Sastry, S.Md. Asadullah, G. Ponticelli, M. Massacesi
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引用次数: 3

摘要

在室温(300 K)和液氮温度下,对Cu(3-AMI)4(ClO4)2和Cu(3-AMI)4(NO3)2[3-AMI = 3-氨基,5-甲基异恶唑]在多晶和溶液形态下进行了EPR研究,以获得立体化学信息和金属-配体键的性质。这些配合物在室温下也能得到Cu(II)的超细线,这在非稀Cu(II)配合物中是罕见的。在上述温度下,这些配合物的多晶样品中没有得到由键合氮形成的配体超细(LHF)结构,从而可以更准确地估计出σ-键强度。在液氮温度下,光谱参数和分辨率的变化可以忽略不计。在LNT得到的Cu(3-AMI)4(ClO4)2的MeCN和吡啶溶液中得到的上述参数与多晶值相当,表明在这些溶剂中溶剂化程度较低。从上述样品在刚性吡啶溶液中的垂直分量上观察到的键合氮的LHF结构,使我们能够比其他情况更准确地计算出σ-键强度。在Cu(3-AMI)4(NO3)2的DMF (N, N ' -二甲基甲酰胺)溶液中形成的物质具有CuO6发色团的特征,表明在上述溶液中溶剂化作用较强。通过计算上述所有情况下Cu(II)基态的4s- s特征来确定轴向场的相对强度。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
EPR studies on Cu(3-amino, 5-methyl isoxazole)4 (ClO4)2 and Cu(3-amino, 5-methyl isoxazole)4 (NO3)2

EPR studies have been carried out on Cu(3-AMI)4(ClO4)2 and Cu(3-AMI)4(NO3)2[3-AMI = 3-amino, 5-methyl isoxazole] in polycrystalline and solution forms both at room (300 K) and liquid nitrogen temperature to obtain stereochemical information and the nature of the metal-ligand bond. Cu(II) hyperfine lines are obtained in these complexes even at room temperature, which is rare for a non-dilute Cu(II) complex. No ligand hyperfine (LHF) structure from bonded nitrogen is obtained in polycrystalline samples of these complexes at the above temperatures to allow the σ-bond strength to be estimated more accurately. The change in the spectral parameters and resolution at liquid nitrogen temperature (LNT) is negligible. The above parameters obtained in MeCN and pyridine solutions of Cu(3-AMI)4(ClO4)2 obtained at LNT are of comparable magnitude with the polycrystalline values indicating less solvation in these solvents. LHF structure from bonded nitrogens observed on the perpendicular component of the above sample in forzen pyridine solution enabled us to calculate the σ-bond strength more accurately than the other cases. The species formed in the DMF (N, N′-dimethylformamide) solution of Cu(3-AMI)4(NO3)2 is characteristic of a CuO6 chromophore indicating stronger solvation in the above solution. The 4s-character in the ground state of Cu(II) in all the above cases was calculated to determine the relative strengths of axial fields.

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