一种混合价态的八核铁氧代吡唑酸盐：通过结构和光谱分析评估电子离域
A mixed-valence octanuclear iron-oxo pyrazolate: assessment of electronic delocalization by structural and spectroscopic analysis.
作者信息
Chakraborty Indranil, Baran Peter, Sanakis Yiannis, Simopoulos Athanassios, Fachini Esteban, Raptis Raphael G
机构信息
Department of Chemistry and the Institute of Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00931-3346.
出版信息
Inorg Chem. 2008 Dec 15;47(24):11734-7. doi: 10.1021/ic801459s.
Abstract
A formally Fe(III)(7)Fe(II) complex, containing an inner Fe(4)O(4)-cubane and four peripheral Fe centers, is derived from the one-electron reduction of its Fe(III)(8) precursor. Spectroscopic analysis of the former reveals that the redox activity of this Fe(8) system is confined within its cubane core. The resulting (Fe(4)O(4))(3+)-cubane, which is valence-delocalized in the NMR, Mössbauer, and IR spectroscopy time scales but valence-trapped in the X-ray photoelectron spectroscopy (XPS) time scale, is better described as a Robin-Day class-II system by the analysis of its near-infrared (NIR) intervalence charge transfer (IVCT) band profile.
摘要
一种形式上为Fe(III)₇Fe(II)的配合物，包含一个内部的Fe₄O₄-立方烷和四个外围铁中心，由其Fe(III)₈前体的单电子还原得到。对前者的光谱分析表明，该Fe₈体系的氧化还原活性局限于其立方烷核心内。所得的(Fe₄O₄)³⁺-立方烷，在核磁共振、穆斯堡尔和红外光谱时间尺度上是价态离域的，但在X射线光电子能谱（XPS）时间尺度上是价态捕获的，通过对其近红外（NIR）价间电荷转移（IVCT）带轮廓的分析，更好地描述为罗宾-戴II类体系。
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