Solvation structures of Manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II), and gallium(III) ions in methanol, ethanol, dimethyl sulfoxide, and trimethyl phosphate as studied by EXAFS and electronic spectroscopies
Solvation structures of Manganese(II), iron(II), cobalt(II), nickel(II), copper(II), zinc(II), and gallium(III) ions in methanol, ethanol, dimethyl sulfoxide, and trimethyl phosphate as studied by EXAFS and electronic spectroscopies
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DOI：
10.1021/jp983799y
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发表时间：
1999-03-11
影响因子：
2.9
通讯作者：
Funahashi, S
中科院分区：
文献类型：
--
作者：
Inada, Y;Hayashi, H;Funahashi, S
用扩展X射线吸收精细结构(EXAFS)谱研究了Mn(II)、Fe(II)、Co(II)、Ni(II)、Cu(II)、Zn(II)和Ga(III)在甲醇(MeOH)、乙醇(EtOH)、二甲基亚砜(DMSO)和磷酸三甲酯(TMP)中的溶剂化结构。在甲醇、乙醇和二甲基亚砜中，所有金属离子的溶剂化结构均为六配位八面体结构，M-O键长与水相似。在体积较大的TMP溶剂中，锌离子在没有配位场稳定的情况下观察到了五配位的溶剂化结构。由于Ga(III)离子上的电荷密度较高，使其在TMP中具有六配位的溶剂化结构，尽管其离子半径比Zn(II)离子小。测量了Mn(II)、Fe(II)、Co(II)、Ni(II)和Cu(II)离子在甲醇、乙醇和二甲基亚砜中的电子吸收光谱。每种金属离子的所有溶液都显示出类似于水中的光谱模式，这与EXAFS测量的结果是一致的。
Solvation structures of the Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Ga(III) ions in methanol (MeOH), ethanol (EtOH), dimethyl sulfoxide (DMSO), and trimethyl phosphate (TMP) have been determined using extended X-ray absorption fine structure (EXAFS) spectroscopy. In MeOH, EtOH, and DMSO, the solvation structures of all metal(II,III) ions are 6-coordinate octahedral as in water, and the M-O bond lengths are similar to those in water. In the bulky solvent TMP, the 5-coordinate solvation structure is observed for the Zn(II) ion without ligand-field stabilization. The Ga(III) ion has the 6-coordinate solvation structure in TMP despite its smaller ionic radius than the Zn(II) ion because of the higher charge density on the Ga(III) ion. In the cases of the Mn(II), Fe(II), Co(II), Ni(II), and Cu(II) ions, the electronic absorption spectra have been measured in MeOH, EtOH, and DMSO. All solutions for each metal(II) ion show a spectral pattern similar to that in water, which is consistent with the results of the EXAFS measurements.