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첨단연성물질 연구단
첨단연성물질 연구단
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Proton diffusion dynamics along a diol as a proton-conducting wire in a photo-amphiprotic model system

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Title
Proton diffusion dynamics along a diol as a proton-conducting wire in a photo-amphiprotic model system
Author(s)
Ye-Jin Kim; Oh-Hoon Kwon
Publication Date
2016-12
Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.18, no.48, pp.32826 - 32839
Publisher
ROYAL SOC CHEMISTRY
Abstract
We investigated the dynamics of excited-state proton transfer (ESPT) of photo-amphiprotic 7-hydroxyquinoline (7HQ) in the presence of a hydrogen (H)-bond bridging diol in a polar aprotic medium. The formation of 1 : 1 H-bonded complexes of 7HQ with various diols of different alkane chain lengths was revealed using steady-state electronic spectroscopy. With femtosecond-resolved fluorescence spectroscopy, cyclic H-bonded 1 : 1 complexes were found to undergo facile ESPT from the acidic enol to the basic imine group of 7HQ via the H-bond bridge. Through quantum chemical calculations, we found that the proton-transfer rate of the well-configured H-bonded complex correlated with the intramolecular H-bond length of a H-bond wiring diol molecule. Noncyclic, singly H-bonded 7HQ with a diol molecule was observed to undergo ESPT once another diol molecule diffuses to the noncyclic complex and accomplishes the formation of a reactive cyclic H-bonded 7HQ–(diol)2 complex, which was evidenced by the observation that the overall proton-transfer rate constant decreases when a longer-chain diol was used as the bridging wire part. The kinetic isotope effect on the proton relay was investigated to confirm that the nature of the activation barrier for the proton diffusion along the wire is isotope-sensitive proton tunnelling, while for the non-cyclic configuration, the isotope-insensitive H-bond bridge formation is a prerequisite for ESPT. © the Owner Societies 2016
URI
https://pr.ibs.re.kr/handle/8788114/3225
ISSN
1463-9076
Appears in Collections:
Center for Soft and Living Matter(첨단연성물질 연구단) > Journal Papers (저널논문)
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