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Title: Excited-state electron transfer in a chromophore-quencher complex. Spectroscopic identification of a redox-separated state

Abstract

The authors report herein the first photophysical studies on Re complexes. In the chromophore-quencher complex fac-[Re(Aqphen)(CO){sub 3}(py-PTZ)]{sup +} (Aqphen is 12,17-dihydronaphtho[2,3-h]dipyrido[3,2-a:2{prime}3{prime}-c]-phenazine-12,17-dione; py-PTZ is 10-(4-picolyl)phenothiazine). Aqphen is a dppz derivative, containing a pendant quinone acceptor at the terminus of a rigid ligand framework. Quinone acceptors are used widely in studies of photoinduced electron and energy transfer. This introduces a derivative third, low-lying, ligand-based {pi}{sup *} acceptor level localized largely on the quinone fragment. Laser flash excitation of fac-[Re(Aqphen)(CO){sub 3}(py-PTZ)]{sup +} (354.7 nm; in 1,2-dichloroethane) results in the appearance of a relatively long-lived transient that decays with {tau}{sub 298K} = 300 ns (k = 3.3 {times} 10{sup 6} s{sup {minus}1}). Application of transient absorption, time-resolved resonance Raman, and time-resolved infrared spectroscopies proves that this transient is the redox-separated state fac-[Re{sup I}(Aqphen{sup {sm_bullet}{minus}})(CO){sub 3}(py-PTZ{sup {sm_bullet}+})]{sup +} in which the excited electron is localized largely on the quinone portion of the Aqphen ligand.

Authors:
; ;  [1]
  1. Univ. Catolica de Chile, Santiago (Chile). Facultad de Quimica; and others
Publication Date:
Sponsoring Org.:
National Science Foundation, Washington, DC (United States); USDOE, Washington, DC (United States)
OSTI Identifier:
682139
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 38; Journal Issue: 12; Other Information: PBD: 14 Jun 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; EXCITED STATES; PHOTOCHEMICAL REACTIONS; QUINONES; DYES; RHENIUM COMPLEXES; ELECTRON TRANSFER

Citation Formats

Lopez, R, Leiva, A M, and Zuloaga, F. Excited-state electron transfer in a chromophore-quencher complex. Spectroscopic identification of a redox-separated state. United States: N. p., 1999. Web. doi:10.1021/ic981050w.
Lopez, R, Leiva, A M, & Zuloaga, F. Excited-state electron transfer in a chromophore-quencher complex. Spectroscopic identification of a redox-separated state. United States. https://doi.org/10.1021/ic981050w
Lopez, R, Leiva, A M, and Zuloaga, F. Mon . "Excited-state electron transfer in a chromophore-quencher complex. Spectroscopic identification of a redox-separated state". United States. https://doi.org/10.1021/ic981050w.
@article{osti_682139,
title = {Excited-state electron transfer in a chromophore-quencher complex. Spectroscopic identification of a redox-separated state},
author = {Lopez, R and Leiva, A M and Zuloaga, F},
abstractNote = {The authors report herein the first photophysical studies on Re complexes. In the chromophore-quencher complex fac-[Re(Aqphen)(CO){sub 3}(py-PTZ)]{sup +} (Aqphen is 12,17-dihydronaphtho[2,3-h]dipyrido[3,2-a:2{prime}3{prime}-c]-phenazine-12,17-dione; py-PTZ is 10-(4-picolyl)phenothiazine). Aqphen is a dppz derivative, containing a pendant quinone acceptor at the terminus of a rigid ligand framework. Quinone acceptors are used widely in studies of photoinduced electron and energy transfer. This introduces a derivative third, low-lying, ligand-based {pi}{sup *} acceptor level localized largely on the quinone fragment. Laser flash excitation of fac-[Re(Aqphen)(CO){sub 3}(py-PTZ)]{sup +} (354.7 nm; in 1,2-dichloroethane) results in the appearance of a relatively long-lived transient that decays with {tau}{sub 298K} = 300 ns (k = 3.3 {times} 10{sup 6} s{sup {minus}1}). Application of transient absorption, time-resolved resonance Raman, and time-resolved infrared spectroscopies proves that this transient is the redox-separated state fac-[Re{sup I}(Aqphen{sup {sm_bullet}{minus}})(CO){sub 3}(py-PTZ{sup {sm_bullet}+})]{sup +} in which the excited electron is localized largely on the quinone portion of the Aqphen ligand.},
doi = {10.1021/ic981050w},
url = {https://www.osti.gov/biblio/682139}, journal = {Inorganic Chemistry},
number = 12,
volume = 38,
place = {United States},
year = {1999},
month = {6}
}