X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions

T. J. Penfold; M. Reinhard; M. H. Rittmann-Frank; I. Tavernelli; U. Rothlisberger; C. J. Milne; P. Glatzel; M. Chergui

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X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions

机译：X射线光谱研究溶剂对亚铁和六氰化铁阴离子的影响

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We present an Fe Kα resonant inelastic X-ray scattering (RIXS) and X-ray emission (XES) study of ferrous and ferric hexacyanide dissolved in water and ethylene glycol. We observe that transitions below the absorption edge show that the solvent has a distinct effect on the valence electronic structure. In addition, both the RIXS and XES spectra show a stabilization of the 2p levels when dissolved in water. Using molecular dynamics simulations, we propose that this effect arises from the hydrogen-bonding interactions between the complex and nearby solvent molecules. This withdraws electron density from the ligands, stabilizing the complex but also causing a slight increase in π-backbonding.

机译：我们介绍了FeKα共振非弹性X射线散射（RIXS）和X射线发射（XES）对溶解在水和乙二醇中的六价铁和六价铁的研究。我们观察到吸收边缘以下的跃迁表明溶剂对价电子结构具有明显的影响。此外，当溶解在水中时，RIXS和XES光谱均显示2p水平的稳定。使用分子动力学模拟，我们认为这种效应是由配合物与附近溶剂分子之间的氢键相互作用引起的。这从配体中撤出电子密度，稳定了络合物，但同时也导致π反向键的轻微增加。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2014年第40期|共8页
作者
T. J. Penfold; M. Reinhard; M. H. Rittmann-Frank; I. Tavernelli; U. Rothlisberger; C. J. Milne; P. Glatzel; M. Chergui;
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正文语种 eng
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X-ray; Spectroscopic; Ferric Hexacyanide Anions;

机译：X射线;光谱;六氰合铁阴离子;

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1. X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions [J] . T. J. Penfold, M. Reinhard, M. H. Rittmann-Frank, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2014,第40期

机译：X射线光谱研究溶剂对亚铁和六氰化铁阴离子的影响
2. Ultrafast photophysics and photochemistry of iron hexacyanides in solution: Infrared to X-ray spectroscopic studies [J] . Chergui M. Coordination chemistry reviews . 2018,第OCTa期

机译：溶液中六氰化铁的超快光物理和光化学：红外到X射线光谱研究
3. Spectroscopic studies on the cation-anion, cation-solvent and anion-solvent interactions in the LiCF3SO3/acetamide complex system [J] . Hu YS, Wang ZX, Li H, Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy . 2005,第3期

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4. Solvent Effects on the Relaxation Dynamics of 7-Aminocoumarins. A Femtosecond Time-Resolved Spectroscopic Study [C] . Mialocq, J.-C., Gustavsson, . 1996

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X-ray Spectroscopic Study of Solvent Effects on the Ferrous and Ferric Hexacyanide Anions

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