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N-芳基-N'-异丙氧基羰基磺酰胺与 DDQ 和 TCNE 的荷移络合物的分光光度和热力学研究。

A spectrophotometric and thermodynamic study of the charge-transfer complexes of N-aryl-N'-isopropyloxycarbonylsulfamides with DDQ and TCNE.

机构信息

Laboratoire de Chimie Physique, Université 08 Mai 45, BP401, Guelma 24000, Algeria.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2013 May;108:55-61. doi: 10.1016/j.saa.2013.01.083. Epub 2013 Feb 9.

Abstract

Molecular charge-transfer complexes of three N-aryl-N'-isopropyloxycarbonylsulfamides derivatives with π-acceptors tetracyanoethylene (TCNE), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), were studied by using zero and second order derivative UV spectrophotometry in different solvents at four different temperatures within the range of 20-35 °C. The stoichiometries of the complexes were found to be 1:1 ratio between donors and acceptors using Job's method. The data were analyzed in terms of their stability constant (K), molar extinction coefficient (εCT), thermodynamic standard reaction quantities (ΔG°, ΔH°, ΔS°), oscillator strength (f), transition dipole moment (μEN) and ionization potential (ID). The results show that the stability constant (K) for the complexes was found to be dependant upon the nature of electron acceptor, electron donor, and polarity of used solvents.

摘要

采用零阶和二阶导数紫外分光光度法,在 20-35°C 的四个不同温度下,在不同溶剂中研究了三种 N-芳基-N'-异丙氧基羰基磺酰胺衍生物与π受体四氰乙烯(TCNE)和 2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)的分子电荷转移络合物。使用 Job 法发现络合物的化学计量比为供体与受体的 1:1 比。根据稳定常数(K)、摩尔消光系数(εCT)、热力学标准反应量(ΔG°、ΔH°、ΔS°)、振子强度(f)、跃迁偶极矩(μEN)和电离势(ID)对数据进行了分析。结果表明,络合物的稳定常数(K)取决于电子受体、电子供体的性质和所用溶剂的极性。

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