Charge transfer vs. proton transfer in the excited-state dynamics of biomimetic pyranoflavylium cations
Journal of Photochemistry and Photobiology(2022)
摘要
Pyranoflavylium cations are synthetic analogues of pyranoanthocyanin, colored pigments, formed from grape anthocyanins during the maturation of red wines. Studies of a series of monosubstituted pyranoflavylium cations, ranging from methoxy (PF+-OMe) to cyano (PF+-CN), have shown that they display fluorescence and form triplet states that sensitize singlet oxygen formation in acidified acetonitrile. In alcohol-water mixtures, they behave as photoacids, undergoing adiabatic excited state proton transfer (ESPT) to water on a picosecond timescale, as confirmed in this report by femtosecond pump-probe spectroscopy. In contrast, the corresponding dimethylamino substituted pyranoflavylium cation (PF+-NMe2) is virtually non-fluorescent under the same conditions and exhibits a long-wavelength absorption band that has been attributed to a charge-transfer (CT) transition. Indeed, pump-probe spectroscopy of PF+-NMe2 in acidified acetonitrile shows ultrafast (<1 ps) formation of a CT state that decays back to the ground state with a 12–13 ps lifetime. In acidified methanol, the initial Franck-Condon CT state (ca. 3 ps lifetime) converts to a 13 ps lifetime CT state analogous to that in acetonitrile. In 50:50 ethanol:water and 30:70 methanol:water mixtures, PF+-NMe2 exhibits a short-lived (3–8 ps) initial CT state, an intermediate lifetime (30 ps) CT state and a much longer lived (130 ps) species attributed to a twisted intramolecular CT state. Thus, in addition to demonstrating that the photophysics of PF+-NMe2 is dominated by CT rather than ESPT, pump-probe spectroscopy provides details of the solvent-dependent dynamics of the CT decay pathways.
更多查看译文
关键词
Pyranoflavylium cations,Pyranoanthocyanins,Charge transfer,Proton transfer,Pump-probe spectroscopy
AI 理解论文
溯源树
样例
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要