Characterization of the Thermal and Photoinduced Reactions of Photochromic Spiropyrans in Aqueous Solution

被引:94
|
作者
Hammarson, Martin [1 ]
Nilsson, Jesper R. [1 ]
Li, Shiming [1 ]
Beke-Somfai, Tamas [1 ]
Andreasson, Joakim [1 ]
机构
[1] Chalmers Univ Technol, Dept Chem & Biol Engn, S-41296 Gothenburg, Sweden
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 2013年 / 117卷 / 43期
基金
欧洲研究理事会; 瑞典研究理事会;
关键词
LOCK-IN DETECTION; PHOTOSWITCHABLE NANOPARTICLES; SOLVENT DEPENDENCE; ENERGY-TRANSFER; MEROCYANINE; LOGIC; SUBSTITUENT; HYDROLYSIS; MECHANISM; KINETICS;
D O I
10.1021/jp408781p
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Six water-soluble spiropyran derivatives have been characterized with respect to the thermal and photoinduced reactions over a broad pH-interval. A comprehensive kinetic model was formulated including the Spiro- and the merocyanine isomers, the respective protonated forms, and the hydrolysis products. The experimental studies on the hydrolysis reaction mechanism were supplemented by calculations using quantum mechanical (QM) models employing density functional theory. The results show that (I) the substitution pattern dramatically influences the pK(a)-values of the protonated forms as well as the rates of the thermal isomerization reactions, (2) water is the nucleophile in the hydrolysis reaction around neutral pH, (3) the phenolate oxygen of the merocyanine form plays a key role in the hydrolysis reaction. Hence, the nonprotonated merocyanine isomer is susceptible to hydrolysis, whereas the corresponding protonated form is stable toward hydrolytic degradation.
引用
收藏
页码:13561 / 13571
页数:11
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