Contribution of NMR spectroscopy to the mechanistic understanding of photochromism

S.Delbaere; J. C.Micheau; J.Berthet; G.Vermeersch

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Contribution of NMR spectroscopy to the mechanistic understanding of photochromism

机译：NMR光谱对光致变色机理的理解

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Along with classical UV-Visible spectroscopy allowing for the determination of intrinsic properties(λmax,ε), multinuclear NMR spectroscopy is a promising and useful tool for studying photochromicreactions. UV irradiation of the initial structure leads to the formation of photoproducts, which can be structurallyidentified by 1D and 2D NMR experiments. The kinetics of thermal back reaction are monitored bydirectly and separately measuring the concentrations of each long-living species at regular time intervalsin NMR spectra. A plausible reaction mechanism can therefore be proposed. Based on this mechanism, thekinetic analysis and the study of the effects of temperature lead to the determination of the kinetic andthermodynamic parameters (rate coefficients, enthalpy and entropy of activation) of the photochromic systemunder investigation. This process has been applied to several photochromic families, spirooxazines andbenzo- and naphtho-pyrans.

机译：与经典的紫外-可见光谱法一起使用以确定固有性质（λmax，ε），多核NMR光谱法是研究光致变色反应的有前途和有用的工具。初始结构的紫外线照射导致形成光产物，可以通过1D和2D NMR实验在结构上进行鉴定。通过在NMR光谱中以固定的时间间隔直接并分别测量每种长寿命物质的浓度，可以监控热逆反应的动力学。因此可以提出合理的反应机理。基于这种机理，通过动力学分析和温度影响的研究，可以确定所研究的光致变色系统的动力学和热力学参数（速率系数，焓和活化熵）。该方法已应用于几种光致变色家族，螺恶嗪和苯并吡喃和萘并吡喃。

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《International Journal of Photoenergy》 |2004年第4期|共8页
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S.Delbaere; J. C.Micheau; J.Berthet; G.Vermeersch;
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Contribution of NMR spectroscopy to the mechanistic understanding of photochromism

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