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Title: Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes

Abstract

Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II) polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and timeresolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II),Rh(III) supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer) excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer) excited state. The details of the photophysics of Ru(II),Rh(III) and Ru(II),Rh(III),Ru(II) systems as probed by steady-state and timeresolved emission spectroscopy will be highlighted.

Authors:
 [1];  [1];  [1];  [1]
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  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1628424
Resource Type:
Accepted Manuscript
Journal Name:
Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 1996-1944
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Materials Science; emission spectroscopy; MLCT light absorbers; polyazine bridging ligands; supramolecular; intramolecular electron transfer

Citation Formats

White, Travis, Arachchige, Shamindri, Sedai, Baburam, and Brewer, Karen. Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes. United States: N. p., 2010. Web. doi:10.3390/ma3084328.
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White, Travis, Arachchige, Shamindri, Sedai, Baburam, & Brewer, Karen. Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes. United States. https://doi.org/10.3390/ma3084328
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White, Travis, Arachchige, Shamindri, Sedai, Baburam, and Brewer, Karen. Wed . "Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes". United States. https://doi.org/10.3390/ma3084328. https://www.osti.gov/servlets/purl/1628424.
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@article{osti_1628424,
title = {Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II),Rh(III) Supramolecular Complexes},
author = {White, Travis and Arachchige, Shamindri and Sedai, Baburam and Brewer, Karen},
abstractNote = {Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II) polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and timeresolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II),Rh(III) supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer) excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer) excited state. The details of the photophysics of Ru(II),Rh(III) and Ru(II),Rh(III),Ru(II) systems as probed by steady-state and timeresolved emission spectroscopy will be highlighted.},
doi = {10.3390/ma3084328},
journal = {Materials},
number = 8,
volume = 3,
place = {United States},
year = {Wed Aug 11 00:00:00 EDT 2010},
month = {Wed Aug 11 00:00:00 EDT 2010}
}
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Photoinitiated Electron Collection at a Metal in a Rhodium-Centered Mixed-Metal Supramolecular Complex
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Synthesis, characterization, and study of the photophysics and photocatalytic properties of the photoinitiated electron collector [{(phen)2Ru(dpp)}2RhBr2](PF6)5
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Spectroscopic investigations of excited states of transition-metal complexes
journal, July 1975

Photophysics and photoredox reactions of ligand-bridged binuclear polypyridyl complexes of ruthenium(II) and of their monomeric analogs
journal, May 1990

  • Kalyanasundaram, K.; Nazeeruddin, M. K.
  • Inorganic Chemistry, Vol. 29, Issue 10
  • DOI: 10.1021/ic00335a026

Photoinitiated Electron Collection at a Metal in a Rhodium-Centered Mixed-Metal Supramolecular Complex
journal, July 2006

  • Elvington, Mark; Brewer, Karen J.
  • Inorganic Chemistry, Vol. 45, Issue 14
  • DOI: 10.1021/ic0602648

Photoinduced Electron Transfer across Oligo- p -phenylene Bridges. Distance and Conformational Effects in Ru(II)−Rh(III) Dyads
journal, July 2007

  • Indelli, Maria Teresa; Chiorboli, Claudio; Flamigni, Lucia
  • Inorganic Chemistry, Vol. 46, Issue 14
  • DOI: 10.1021/ic700430u

Ruthenium(II)-Polyazine Light Absorbers Bridged to Reactive cis -Dichlororhodium(III) Centers in a Bimetallic Molecular Architecture
journal, December 2008

  • Zigler, David F.; Wang, Jing; Brewer, Karen J.
  • Inorganic Chemistry, Vol. 47, Issue 23
  • DOI: 10.1021/ic8007602

Photoinduced Electron and Energy Transfer in Rigidly Bridged Ru(II)−Rh(III) Binuclear Complexes
journal, January 1996

  • Indelli, Maria Teresa; Scandola, Franco; Collin, Jean-Paul
  • Inorganic Chemistry, Vol. 35, Issue 2
  • DOI: 10.1021/ic950745j

Effect of Delocalization and Rigidity in the Acceptor Ligand on MLCT Excited-State Decay
journal, January 1996

  • Treadway, Joseph A.; Loeb, Barbara; Lopez, Rosa
  • Inorganic Chemistry, Vol. 35, Issue 8
  • DOI: 10.1021/ic950961s

Photoinduced Electron Transfer in Ruthenium(II)−Rhodium(III) Terpyridine Dyads
journal, September 1997

  • Indelli, M. T.; Scandola, F.; Flamigni, L.
  • Inorganic Chemistry, Vol. 36, Issue 19
  • DOI: 10.1021/ic9702577

A Tridentate-Bridged Ruthenium−Rhodium Complex as a Stereochemically Defined Light-Absorber−Electron-Acceptor Dyad
journal, July 1998

  • Lee, Jae-Duck; Vrana, Lisa M.; Bullock, Elizabeth R.
  • Inorganic Chemistry, Vol. 37, Issue 14
  • DOI: 10.1021/ic970892c

Excited-state interactions in ligand-bridged chromophore-quencher complexes containing rhodium(III) and ruthenium(II) polypyridyl units
journal, July 1992

  • Kalyanasundaram, K.; Graetzel, M.; Nazeeruddin, M. K.
  • The Journal of Physical Chemistry, Vol. 96, Issue 14
  • DOI: 10.1021/j100193a041

Photoinitiated Electron Collection in a Mixed-Metal Trimetallic Complex of the Form {[(bpy)2Ru(dpb)]2IrCl2}(PF6)5 (bpy = 2,2'-Bipyridine and dpb = 2,3-Bis(2-pyridyl)benzoquinoxaline)
journal, June 1994

  • Molnar, Sharon M.; Nallas, Girlie; Bridgewater, Jon S.
  • Journal of the American Chemical Society, Vol. 116, Issue 12
  • DOI: 10.1021/ja00091a026

Mechanism of the formation of dihydrogen from the photoinduced reactions of poly(pyridine)ruthenium(II) and poly(pyridine)rhodium(III) complexes
journal, January 1981

  • Chan, S. -F.; Chou, Mei; Creutz, Carol
  • Journal of the American Chemical Society, Vol. 103, Issue 2
  • DOI: 10.1021/ja00392a022

Photocatalytic Hydrogen Production from Water Employing A Ru, Rh, Ru Molecular Device for Photoinitiated Electron Collection
journal, September 2007

  • Elvington, Mark; Brown, Jared; Arachchige, Shamindri M.
  • Journal of the American Chemical Society, Vol. 129, Issue 35
  • DOI: 10.1021/ja073123t

Long-range coupling in a mixed-valence diruthenium complexes containing bis-terpyridine ligands of various lengths as bridges
journal, January 1993

  • Collin, Jean-Paul; Lainé, Philippe; Launay, Jean-Pierre
  • J. Chem. Soc., Chem. Commun., Issue 5
  • DOI: 10.1039/c39930000434

The energy gap law for radiationless transitions in large molecules
journal, February 1970

Chemical and Electrochemical Electron-Transfer Theory
journal, October 1964

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