Effect of Viscosity on the Spin Exchange of TCNE and TEMPO Radicals with Iron(III) Acetylacetonate

Hussain T; Rasmussen K; Grampp G; Kokorin AI

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Effect of Viscosity on the Spin Exchange of TCNE and TEMPO Radicals with Iron(III) Acetylacetonate

机译：粘度对乙酰丙酮铁（III）自旋交换TCNE和TEMPO自由基的影响

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The spin exchange of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and the radical anion of tetracyanoethene (TCNE), with iron acetylacetonate, Fe(acac)(3), was investigated as a function of solvent viscosity and temperature by X-band EPR spectroscopy. Acetone, methanol, ethanol, 1-propanol, 1-pentanol, 1-hexanol, 1-octanol, and chloroform were used as solvents because they provide a wide range of viscosity. The spin exchange rate constants measured in the different solvents ranged from 3 x 10(8) to 8 x 10(9) M-1 s(-1), and from 7 x 10(8) to 1 x 10(10) M-1 s(-1) for the TEMPO/Fe(acac)(3) and the TCNE/Fe(acac)(3) systems, respectively. The spin exchange rate constants, k (e), are compared with the corresponding diffusion rate constants. It was found that the k (e) values correlate well with those of diffusion and hence the intermolecular spin exchange is strongly diffusion-controlled. The activation energies and pre-exponential factors are calculated from the Arrhenius plots.

机译：研究了2,2,6,6-四甲基哌啶-1-氧基（TEMPO）和四氰基乙烯（TCNE）与乙酰丙酮铁Fe（acac）（3）的自旋交换与溶剂粘度的关系X波段EPR光谱分析温度。丙酮，甲醇，乙醇，1-丙醇，1-戊醇，1-己醇，1-辛醇和氯仿被用作溶剂，因为它们具有广泛的粘度范围。在不同溶剂中测得的自旋交换速率常数范围为3 x 10（8）至8 x 10（9）M-1 s（-1），以及7 x 10（8）至1 x 10（10）M对于TEMPO / Fe（acac）（3）和TCNE / Fe（acac）（3）系统，分别为-1 s（-1）。将自旋交换速率常数k（e）与相应的扩散速率常数进行比较。发现k（e）值与扩散的相关性很好，因此分子间自旋交换受到强烈的扩散控制。活化能和指数前因子是根据阿伦尼乌斯曲线计算的。

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《Applied Magnetic Resonance》 |2009年第1期|共10页
作者
Hussain T; Rasmussen K; Grampp G; Kokorin AI;
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正文语种 eng
中图分类磁性弛豫及共振现象;
关键词
NITROXIDE FREE-RADICALS; LINE-SHAPE CHANGES; ELECTRON EXCHANGE; HIGH-PRESSURES; ESR; RESONANCE; EPR; COMPLEXES; LIQUIDS; SOLVENT;

机译：硝基氧自由基;线型变化;电子交换;高压;ESR;共振;EPR;复合物;液体;溶剂;

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1. Effect of Viscosity on the Spin Exchange of TCNE and TEMPO Radicals with Iron(III) Acetylacetonate [J] . Hussain T, Rasmussen K, Grampp G, Applied Magnetic Resonance . 2009,第1期

机译：粘度对乙酰丙酮铁（III）自旋交换TCNE和TEMPO自由基的影响
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Effect of Viscosity on the Spin Exchange of TCNE and TEMPO Radicals with Iron(III) Acetylacetonate

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