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Lookup NU author(s): Dr Eimer TuiteORCiD
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Picosecond time-resolved resonance Raman (picosecond-TR3) spectroscopy has been used to conduct an extensive photophysical characterization of the "light- switch" complex [Ru(phen)(2)dppz](2+) as a function of environment, in which studies have been carried out in aqueous and nonaqueous media and in DNA. The results are considered in rotation to a previous report describing "environment-sensitive" lowest triplet MLCT states. Vibrational marker features and enhancement patterns were used to determine the rapid progression (< 20 ps) between two triplet MLCT states in aqueous environment, followed by subnanosecond, nonradiative deactivation to the ground state. In nonaqueous environment, the long-lived, emissive triplet MLCT state is spectrally identified as the short-lived first triplet MLCT state observed in water, in agreement with the earlier proposed mechanism. The present data are shown to correlate well with previous nanosecond RR findings for the complex in each environment. Interestingly, a "precursor state" has been identified upon excitation in both nonaqueous solvent and in DNA, which precedes the triplet MLCT state, and the lifetime of which appears to be environment dependent. Observation of this state is discussed in relation to other recent femtosecond spectroscopic studies on this complex.
Author(s): Coates CG, Olofsson J, Coletti M, McGarvey JJ, Onfelt B, Lincoln P, Norden B, Tuite E, Matousek P, Parker AW
Publication type: Article
Publication status: Published
Journal: Journal of Physical Chemistry B
Year: 2001
Volume: 105
Issue: 50
Pages: 12653-12664
ISSN (print): 1520-6106
ISSN (electronic): 1520-5207
Publisher: American Chemical Society
URL: http://dx.doi.org/10.1021/jp0127115
DOI: 10.1021/jp0127115
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