电子顺磁共振
化学
氢键
激进的
一氧化氮介导的自由基聚合
红外光谱学
光化学
超精细结构
光谱学
溶剂
氢
物理化学
分子
有机化学
核磁共振
聚合物
聚合
自由基聚合
物理
量子力学
作者
Paola Franchi,Marco Lucarini,Pamela Pedrielli,Gian Franco Pedulli
出处
期刊:ChemPhysChem
[Wiley]
日期:2002-09-16
卷期号:3 (9): 789-793
被引量:62
标识
DOI:10.1002/1439-7641(20020916)3:9<789::aid-cphc789>3.0.co;2-z
摘要
The equilibrium constants for the formation of hydrogen-bonded complexes with phenol, benzyl alcohol and diphenyl amine of a persistent nitroxide radical (TEMPO) have been measured for the first time by IR spectroscopy in solution. By making use of the data obtained with IR measurements it was possible to quantitatively determine the effect of hydrogen bonding on the nitrogen hyperfine-splitting constant. On this basis it is shown that EPR spectroscopy can be used as an alternative to IR spectroscopy for the determination of the thermodynamic parameters of hydrogen bond formation with nitroxides by following the dependence of the experimental EPR nitrogen hyperfine splitting of these radicals upon changing the nature of the solvent. The experimental data obtained from both IR and EPR spectroscopy indicate that nitroxides are versatile hydrogen bond acceptors giving hydrogen bonds of strength similar to that of ethers or esters. The corresponding Abraham's beta 2H values have been determined as 0.46.
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