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Picosecond Kerr-gated time-resolved resonance Raman spectroscopy of the [Ru(phen)(2)dppz](2+) interaction with DNA

Lookup NU author(s): Dr Eimer TuiteORCiD

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Abstract

To investigate the basis of the 'light-switch' effect, the solvent dependence of the Kerr-gated picosecond-time resolved resonance Raman (TR3) spectra of [Ru(bpy),dppz](2+), [Ru(phen)(2)dppz](2+), and the modified complex [Ru(phen)(2)cpdppzOMe](2+) and a dimer [mu-C4(cpdppz)(2)-(phen)(4)Ru-2](4+) were studied. The investigation focussed on comparing the behaviour of [Ru(phen)(2)dppz](2+) in acetonitrile, ethanol, H2O, D2O, and DNA. The data are consistent with a model wherein excitation induces metal-to-ligand charge transfer (MLCT) to any of the ligands (termed the 'precursor' state) which, by interligand electron transfer (ILET), produces an excited state localised on the dppz ligand, MLCT1. In water this state relaxes with a characteristic time of similar to6 ps to a non-emissive state (MLCT2). The TR3 spectra in water, acetonitrile and DNA are all distinctly different. However. the early (4 ps) water spectrum resembles the spectrum in DNA. This interesting observation suggests that the DNA-bound excited state of the complex can be thought of as a model for the initial, poorly solvated state in water. (C) 2002 Elsevier Science Inc. All rights reserved.


Publication metadata

Author(s): Tuite E; Olofsson J; Onfelt B; Lincoln P; Norden B; Matousek P; Parker AW

Publication type: Article

Publication status: Published

Journal: Journal of Inorganic Biochemistry: 10th International Conference on Bioinorganic Chemistry

Year: 2002

Volume: 91

Issue: 1

Pages: 286-297

ISSN (print): 0162-0134

ISSN (electronic): 1873-3344

Publisher: Elsevier Inc.

URL: http://dx.doi.org/10.1016/S0162-0134(02)00466-X

DOI: 10.1016/S0162-0134(02)00466-X


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