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Title: Application of transient infrared spectroscopy to intramolecular energy transfer in [(phen) (CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +]

Abstract

Significant advances have been made in the design and characterization of molecular assemblies, which, when photolyzed, undergo intramolecular electron or energy transfer. Time-resolved resonance Raman spectroscopy has been successfully applied to the study of excited states and molecular assemblies, but time-resolved infrared spectroscopy is particularly well-suited for complexes containing ligands such as CO or CN. Unlike the transient Raman experiment, infrared spectroscopy does not rely on resonance enhancement in the excited state since the metal-CO and -CN stretching vibrations have high oscillator strengths, providing high sensitivity. We describe here a novel application of the technique to the elucidation of intramolecular energy transfer in the ligand-bridged complex [(phen)(CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +] (phen is 1, 10-phenanthroline; bpy is 2,2'-bipyridine). These results show that the transient infrared technique can be a powerful tool for the elucidation of oxidation state and mechanisms involving photochemical intermediates by direct observation of ligand vibrations. 15 refs., 2 figs.

Authors:
;  [1]; ; ; ;  [2]; ;  [3]
  1. Univ. of North Carolina, Chapel Hill, NC (United States)
  2. Los Alamos National Lab., NM (United States)
  3. Universita di Ferrara (Italy)
Publication Date:
OSTI Identifier:
7302072
DOE Contract Number:  
FG05-86ER13633
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (United States)
Additional Journal Information:
Journal Volume: 115:23; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; RHENIUM COMPLEXES; ENERGY TRANSFER; INFRARED SPECTRA; RUTHENIUM COMPLEXES; LASERS; PHOTOLYSIS; REACTION INTERMEDIATES; CHEMICAL REACTIONS; COMPLEXES; DECOMPOSITION; PHOTOCHEMICAL REACTIONS; SPECTRA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400500 - Photochemistry; 400102 - Chemical & Spectral Procedures

Citation Formats

Schoonover, J R, Myer, T J, Gordon, K C, Woodruff, W H, Peterson, K A, Dyer, R B, Argazzi, R, and Bignozzi, C A. Application of transient infrared spectroscopy to intramolecular energy transfer in [(phen) (CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +]. United States: N. p., 1993. Web. doi:10.1021/ja00076a070.
Schoonover, J R, Myer, T J, Gordon, K C, Woodruff, W H, Peterson, K A, Dyer, R B, Argazzi, R, & Bignozzi, C A. Application of transient infrared spectroscopy to intramolecular energy transfer in [(phen) (CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +]. United States. https://doi.org/10.1021/ja00076a070
Schoonover, J R, Myer, T J, Gordon, K C, Woodruff, W H, Peterson, K A, Dyer, R B, Argazzi, R, and Bignozzi, C A. 1993. "Application of transient infrared spectroscopy to intramolecular energy transfer in [(phen) (CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +]". United States. https://doi.org/10.1021/ja00076a070.
@article{osti_7302072,
title = {Application of transient infrared spectroscopy to intramolecular energy transfer in [(phen) (CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +]},
author = {Schoonover, J R and Myer, T J and Gordon, K C and Woodruff, W H and Peterson, K A and Dyer, R B and Argazzi, R and Bignozzi, C A},
abstractNote = {Significant advances have been made in the design and characterization of molecular assemblies, which, when photolyzed, undergo intramolecular electron or energy transfer. Time-resolved resonance Raman spectroscopy has been successfully applied to the study of excited states and molecular assemblies, but time-resolved infrared spectroscopy is particularly well-suited for complexes containing ligands such as CO or CN. Unlike the transient Raman experiment, infrared spectroscopy does not rely on resonance enhancement in the excited state since the metal-CO and -CN stretching vibrations have high oscillator strengths, providing high sensitivity. We describe here a novel application of the technique to the elucidation of intramolecular energy transfer in the ligand-bridged complex [(phen)(CO)[sub 3]Re[sup I](NC) Ru[sup II](CN) (bpy)[sub 2]][sup +] (phen is 1, 10-phenanthroline; bpy is 2,2'-bipyridine). These results show that the transient infrared technique can be a powerful tool for the elucidation of oxidation state and mechanisms involving photochemical intermediates by direct observation of ligand vibrations. 15 refs., 2 figs.},
doi = {10.1021/ja00076a070},
url = {https://www.osti.gov/biblio/7302072}, journal = {Journal of the American Chemical Society; (United States)},
issn = {0002-7863},
number = ,
volume = 115:23,
place = {United States},
year = {Wed Nov 17 00:00:00 EST 1993},
month = {Wed Nov 17 00:00:00 EST 1993}
}