Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 119, Issue 17, Pages 3986-3994Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b01737
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Funding
- Natural Sciences and Engineering Council of Canada
- Canadian Foundation for Innovation
- Nova Scotia Research and Innovation Trust
- Acadia University
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The photophysicS of a Series of Ru(II) dyads based on the 2-(1-pyrerry1)-IH-imidazo[42,5-f][1,10]-phenanthroline ligand was investigated. The ability of these metal coinplexes to intercalate DNA and induce cell death upon photoactivation makes them attractive photosensitizers for a range of photobiological applications, Including photodynamic therapy. In the present study, time-resolved transient absorption and emission spectroscopy were used to Interrogate the photoinduced processes that follow metal-to-ligand charge transfer excitation of the complexes in solution. It Was found that energy transfer to pyrene-localized intraligand triplet states, facilitated by torsional motion of the pyrene moiety relative to the imidazo[4,5-f] [1,10]phenanthroline ligand was an important relaxation pathway governing the photophysical dynamics RI this class of compounds. Biphasic decay kinetics were assigned to spontaneous (pre-equilibrium) and delayed emission, arising from an equilibrium established between (MLCT)-M-3 and (IL)-I-3 states. TDDFT calculations supported these interpretations.
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