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Ligand-Specific Charge Localization in the MLCT Excited State of Ru(bpy)_2(dpphen)^(2+) Monitored by Time-Resolved Resonance Raman Spectroscopy

Turro, Claudia and Bossmann, Stefan H. and Leroi, George E. and Barton, Jacqueline K. and Turro, Nicholas J. (1994) Ligand-Specific Charge Localization in the MLCT Excited State of Ru(bpy)_2(dpphen)^(2+) Monitored by Time-Resolved Resonance Raman Spectroscopy. Inorganic Chemistry, 33 (7). pp. 1344-1347. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180413-144638081

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Abstract

Time-resolved resonance Raman spectroscopy has been employed to examine the location of the promoted electron in the metal-to-ligand charge-transfer (MLCT) excited state of Ru(bpy)_2(dpphen)^(2+) (bpy) = 2,2'-bipyridine; dpphen = 4,7-diphenyl-1,10-phenanthroline). Variations in the environment about Ru(bpy)_2(dpphen)^(2+) shift the localization of charge in the MLCT excited state from bpy in neutral micelles (Brij 35) to dpphen in the presence of DNA and anionic surfactants (C_(12)H_(25)OSO_3Na, C_(10)H_(23)OSO_3Na, and C_8H_(21)OSO_3Na), whereas in water the electron is localized on both ligands. The shifts in the electronic absorption spectrum and the dependence of the ground-state resonance Raman (rR) signal with excitation wavelengths coincident with the high- and low-energy sides of the MLCT absorption band are consistent with a lowering of the energy of the Ru(II)-dpphen transition with respect to that of bpy in anionic micelles.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/ic00085a022DOIArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Alternate Title:Ligand-Specific Charge Localization in the MLCT Excited State of Ru(bpy)2(dpphen)2+ Monitored by Time-Resolved Resonance Raman Spectroscopy
Additional Information:© 1994 American Chemical Society. Received May 7, 1993. C.T. thanks the Jane Coffin Childs Memorial Fund for Medical Research for a fellowship. This investigation was aided by a grant from the Jane Coffin Childs Memorial Fund for Medical Research. Further support was provided by the Deutsche Forschungsgemeinschaft (S.H.B.) and the National Institutes of Health (G.E.L.). N.J.T. thanks the National Science Foundation and J.K.B. thanks the NIH for generous support of this research. We thank the MSU LASER Laboratory for use of facilities to collect CW resonance Raman spectra.
Funders:
Funding AgencyGrant Number
Jane Coffin Childs Memorial Fund for Medical ResearchUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)UNSPECIFIED
NIHUNSPECIFIED
NSFUNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20180413-144638081
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180413-144638081
Official Citation:Ligand-Specific Charge Localization in the MLCT Excited State of Ru(bpy)2(dpphen)2+ Monitored by Time-Resolved Resonance Raman Spectroscopy Claudia Turro, Stefan H. Bossmann, George E. Leroi, Jacqueline K. Barton, and Nicholas J. Turro Inorganic Chemistry 1994 33 (7), 1344-1347 DOI: 10.1021/ic00085a022
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85849
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:13 Apr 2018 22:05
Last Modified:03 Oct 2019 19:36

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