Verma, Sandeep ; Aute, Sunil ; Das, Amitava ; Ghosh, Hirendra N. (2016) Proton-coupled electron transfer in a hydrogen-bonded charge-transfer complex Journal of Physical Chemistry B, 120 (41). pp. 10780-10785. ISSN 1520-6106
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Official URL: http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.6b060...
Related URL: http://dx.doi.org/10.1021/acs.jpcb.6b06032
Abstract
A proton-coupled electron transfer (PCET) reaction in a hydrogen-bonded charge-transfer (CT) complex of 4-([2,2′-bipyridin]-4-yl)phenol (bpy-phenol) with a F– ion has been investigated by ultrafast time-resolved transient absorption spectroscopy. The phenolic receptor molecule, bpy-phenol, binds to the F– ion through a hydrogen bond and senses the F– ion via the Stokes-shifted CT band. Upon photoexcitation, CT from the phenol residue to the bpy residue promotes proton transfer from the phenol radical cation (ArOH•+) to the fluoride ion at ultrafast time scales of <150 fs (instrument response function limited) and 3 ps, separately. The fast and slow proton-transfer times are linked to two different types of hydrogen-bonding networks between the phenol residue and fluoride ion. Crystalline water in the fluoride salt hydrates mediates the proton-transfer reaction. This work demonstrates the participation of a hydrogen-bonded water bridge within a PCET reaction in a water-restricted environment.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 102187 |
Deposited On: | 25 Jan 2017 04:08 |
Last Modified: | 25 Jan 2017 04:08 |
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