期刊
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
卷 304, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.saa.2023.123294
关键词
Time-resolved spectroscopy; Excited state dynamics; Proton transfer; Schiff base
类别
The proton transfer dynamics of Schiff bases are investigated in this study, focused on the excited state intramolecular proton transfer (ESIPT) process of photochromic salicylaldehyde azine (SAA) in solutions. The ESIPT process is found to occur within <200 fs, followed by vibrational relaxation and isomerization processes. These processes are notably influenced by the polarity of the solvents.
The proton transfer dynamics of Schiff bases are of great importance due to the application potential. The excited state intramolecular proton transfer (ESIPT) of photochromic salicylaldehyde azine (SAA) in solutions was investigated by experimental and computational methods. Two distinguished spectral bands are observed in transient absorption spectra upon the photoexcitation with 400 nm. From the delayed stimulated emission signals, the ESIPT process is determined to be within <200 fs. Subsequently, the photoprotonated products undergo the vibrational relaxation with several picoseconds and the following isomerization with tens of picoseconds. These processes are significantly affected by the polarity of the solvents. The longest component with nanosecond scale can be explained to the relaxation to the enol structure. According to our observations, the SAA molecules with symmetric double-hydrogen-bonding-centers undergo single proton transfer rather than double proton transfer and subsequent intramolecular isomerization.
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