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Excited state intramolecular proton transfer of 1,2-dihydroxyanthraquinone by femtosecond transient absorption spectroscopy

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Abstract
1,2-Dihydroxyanthraquinone (alizarin) shows dual emission bands with a large Stokes shift from a "locally-excited (LE)" and "proton-transferred (PT)" tautomers in the excited state. Excited state intramolecular proton transfer (ESIPT) reaction of alizarin is tunable by changing concentration, solvent polarity, excitation wavelength, and etc. ESIPT reaction of alizarin in the excited state was investigated by steady-state absorption/emission spectroscopy and femtosecond transient absorption spectroscopy. In ethanol solution, the lifetime of PT tautomer of alizarin was measured as 87 ps, in addition to 0.35 and 8.3 ps vibrational cooling dynamics for the LE and PT tautomers of alizarin, respectively. In binary mixtures of ethanol and water, the excited state dynamics became more complicated; the LE and PT tautomers appeared to decay with 8.9 and 30.8 ps lifetimes, which is much shorter compared to the lifetime of the PT tautomer in ethanol. A long-lived nonradiative state in the excited states of alizarin was found as well, which was proposed as a "trapped" state with tightly hydrogen-bonded water molecules. The ESIPT reaction of alizarin was blocked in a 1:1 mixture of ethanol-water due to strong hydrogen bonding between water molecules and alizarin, which was further confirmed by the efficient coupling of alizarin to TiO2 nanoparticles in the 1:1 binary mixture of ethanol-water. (C) 2015 Elsevier B.V. All rights reserved.
Author(s)
Lee, SebokLee, JaebeomPang, Yoonsoo
Issued Date
2015-11
Type
Article
DOI
10.1016/j.cap.2015.08.017
URI
https://scholar.gist.ac.kr/handle/local/14518
Publisher
ELSEVIER SCIENCE BV
Citation
CURRENT APPLIED PHYSICS, v.15, no.11, pp.1492 - 1499
ISSN
1567-1739
Appears in Collections:
Department of Chemistry > 1. Journal Articles
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