Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 16, Issue 36, Pages 19141-19155Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4cp02359e
Keywords
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Funding
- EPSRC
- Ramsay Memorial Fellowship Trust
- European Research Council under the European Union [258990]
- EPSRC [EP/J006602, EP/G006792/1, EP/H003401, EP/J007153]
- ERC [247450]
- Royal Society for a University Research Fellowship
- Engineering and Physical Sciences Research Council [EP/J007145/1, EP/J007153/1, EP/J006602/1, EP/G006792/1] Funding Source: researchfish
- Medical Research Council [G0701062] Funding Source: researchfish
- EPSRC [EP/J006602/1, EP/J007153/1, EP/J007145/1] Funding Source: UKRI
- MRC [G0701062] Funding Source: UKRI
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Mechanistic insight into the photo-induced solvent substitution reaction of cis-Pu(bipyridine)(2)(nicotinamide)(2)](2+) (1) is presented. Complex 1 is a photoactive species, designed to display high cytotoxicity following irradiation, for potential use in photodynamic therapy (photochemotherapy). In Ru(m) complexes of this type, efficient population of a dissociative triplet metal-centred ((MC)-M-3) state is key to generating high quantum yields of a penta-coordinate intermediate (PCI) species, which in turn may form the target species: a mono-aqua photoproduct [Ru(bipyridine)(2)(nicotinamide)(H2O)](2+) (2). Following irradiation of 1, a thorough kinetic picture is derived from ultrafast UV/Vis transient absorption spectroscopy measurements, using a 'target analysis' approach, and provides both timescales and quantum yields for the key processes involved. We show that photoactivation of 1 to 2 occurs with a quantum yield >0.36, all within a timeframe of 400 ps. Characterization of the excited states involved, particularly the nature of the PCI and how it undergoes a geometry relaxation to accommodate the water ligand, which is a keystone in the efficiency of the photoactivation of 1, is accomplished through state-of-the-art computation including complete active space self-consistent field methods and time-dependent density functional theory. Importantly, the conclusions here provide a detailed understanding of the initial stages involved in this photoactivation and the foundation required for designing more efficacious photochemotherapy drugs of this type.
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