Mixed-Valence States of Orthorhombic [Fe3O(C6F5COO)6(C5H5N)3]·CH2Cl2 Characterized by X-ray Crystallography and 57Fe Mössbauer Spectroscopy: Comparison with a Hexagonal Polymorph
Mixed-Valence States of Orthorhombic [Fe3O(C6F5COO)6(C5H5N)3]·CH2Cl2 Characterized by X-ray Crystallography and 57Fe Mössbauer Spectroscopy: Comparison with a Hexagonal Polymorph
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X 射线晶体学和 57Fe 穆斯堡尔谱表征斜方晶系 [Fe3O(C6F5COO)6(C5H5N)3]·CH2Cl2 的混合价态：与六方多晶型物的比较
DOI：
10.1246/bcsj.20160320
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发表时间：
2017
影响因子：
4
通讯作者：
Masashi Takahashi
中科院分区：
文献类型：
--
作者：
Y. Sakai;Ryo Ogiso;T. Kawasaki;T. Kitazawa;T. Nakamoto;T. Takayama;Masashi Takahashi
本文报道了以二氯甲烷为溶剂分子的混价三核五氟苯甲酸铁的晶型结构[Fe3O(C6F5COO)6(C5H5N)3]·CH2Cl2(o-1)，并经123和300K下的单晶X射线分析证实。中心Fe3O部分的Fe-O键长不同。这与我们以前报道的具有D3h局域对称性的六角形(h-1)相反。1 O-1的57Fe穆斯堡尔谱显示，在78-300K之间，由高自旋Fe(III)和高自旋Fe(II)原子组成的价陷态，面积比为2/1到3/1，与h-1的价脱陷态(平均)高于∼90K的结果完全相反。
An orthorhombic form of polymorphs of mixed-valence trinuclear iron pentafluorobenzoate containing dichloromethane as a crystal solvent molecule, [Fe3O(C6F5COO)6(C5H5N)3]·CH2Cl2 (o-1), was newly prepared and confirmed by single crystal X-ray analysis at 123 and 300 K. Three bond lengths of Fe–O in the central Fe3O moiety are not identical, which is in contrast to our previously reported hexagonal form (h-1) having D3h local symmetry.1 57Fe Mossbauer spectra of o-1 showed a valence-trapped state consisting of high-spin Fe(III) and high-spin Fe(II) atoms with an area ratio of 2/1 to 3/1 between 78 and 300 K, being in complete contrast to those of h-1 with the valence-detrapped (averaged) state above ∼90 K. The present findings are consistently explained from the viewpoints of the crystal and molecular structures.