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HERO ID
1037905
Reference Type
Journal Article
Title
On the Role of Hydrogen Bonds in Photoinduced Electron-Transfer Dynamics between 9-Fluorenone and Amine Solvents
Author(s)
Ghosh, HN; Adamczyk, K; Verma, S; Dreyer, J; Nibbering, ET
Year
2012
Is Peer Reviewed?
Yes
Journal
Chemistry: A European Journal
ISSN:
0947-6539
EISSN:
1521-3765
Volume
18
Issue
16
Page Numbers
4930-4937
Language
English
PMID
22389093
DOI
10.1002/chem.201102994
Web of Science Id
WOS:000302354500020
Abstract
Using ultrafast fluorescence upconversion and mid-infrared spectroscopy, we explore the role of hydrogen bonds in the photoinduced electron transfer (ET) between 9-fluorenone (FLU) and the solvents trimethylamine (TEA) and dimethylamine (DEA). FLU shows hydrogen-bond dynamics in the methanol solvent upon photoexcitation, and similar effects may be anticipated when using DEA, whereas no hydrogen bonds can occur in TEA. Photoexcitation of the electron-acceptor dye molecule FLU with a 400 nm pump pulse induces ultrafast ET from the amine solvents, which is followed by 100 fs IR probe pulses as well as fluorescence upconversion, monitoring the time evolution of marker bands of the FLU S(1) state and the FLU radical anion, and an overtone band of the amine solvent, marking the transient generation of the amine radical cation. A comparison of the experimentally determined forward charge-separation and backward charge-recombination rates for the FLU-TEA and FLU-DEA reaction systems with the driving-force dependencies calculated for the forward and backward ET rates reveals that additional degrees of freedom determine the ET reaction dynamics for the FLU-DEA system. We suggest that hydrogen bonding between the DEA molecules plays a key role in this behaviour.
Keywords
amines; donor-acceptor systems; electron transfer; hydrogen bonds; IR spectroscopy
Tags
IRIS
•
Methanol (Non-Cancer)
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