0000000000422806
AUTHOR
Viivi Lehtovuori
Study of Mechanisms of Light-Induced Dissociation of Ru(dcbpy)(CO)2I2 in Solution down to 20 fs Time Resolution
Mechanisms of the light-induced ligand exchange reaction of (trans-I) Ru(dcbpy)(CO)2I2 (dcbpy = 4,4'-dicarboxylic acid-2,2'-bipyridine) in ethanol have been studied by transient absorption spectroscopy. Ultraviolet 20 fs excitation pulses centered at 325 nm were used to populate a vibrationally hot excited pi bipyridyl state of the reactant that quickly relaxes to a dissociative Ru-I state resulting in the release of one of the carbonyl groups. Quantum yield measurements have indicated that about 40% of the initially exited reactant molecules form the final photoproduct. A 62 fs rise component in the transient absorption (TA) signal was observed at all probe wavelengths in the visible regio…
Transient absorption studies of the Ru(dcbpy)2(NCS)2 excited state and the dye cation on nanocrystalline TiO2 film
We have measured dynamics of the Ru(dcbpy)2(NCS)2 [dcbpy = 4,4′-dicarboxy-2,2′-bipyridine] excited state and the dye cation on nanocrystalline TiO2 film in the wavelength region 700–900 nm. The dye in ethanol solution and Ru(dcbpy)2(NCS)2 sensitized nanocrystalline Al2O3 films were used as non-injecting reference samples for excited state identification. For TiO2/Ru(dcbpy)2(NCS)2 film the `reactant' decay and `product' formation kinetics observed at different probe wavelengths showed that the resolved transient absorption picosecond components (1.1±0.2), (12±2) and (100±5) ps are related to electron injection from the excited states of the dye to the semiconductor TiO2.
Ultrafast energy transfer in dansylated POPAM–eosin complexes
Abstract Excitation energy transfer (EET) in dendritic host–guest complexes has been studied. Three generations G2, G3 and G4 of dansyl substituted poly(propyleneamine) dendrimers (POPAM) were complexed with a fluorescent dye eosin in chloroform solution. Arrival of excitation from dansyls to eosin was monitored by femtosecond transient absorption spectroscopy. EET rates from the dansyls to eosin(s) are characterised by two time constants 1 ps and 6 ps independent of dendrimer generation. Relaxation processes in eosin were clearly faster when complexed with dendrimer than in solution. As several eosins are bound to G3 and G4 dendrimers, besides host–guest interaction, also eosin–eosin inter…
Transient Midinfrared Study of Light Induced Dissociation Reaction of Ru(dcbpy)(CO)2I2 in Solution
Illumination of Ru(dcbpy)I2(CO)2 (dcbpy = 4,4‘-dicarboxy-2,2‘-bipyridine) with (near) ultraviolet light induces dissociation of one of the CO groups of the complex. In solution the opened coordination site of the metal is occupied by a solvent molecule. In the present study the kinetics of the ligand exchange reaction has been studied in solution with femtosecond time resolution by probing the CO stretching vibrations of the reactant and the product molecules Ru(dcbpy)I2(CO)(EtOH) in the infrared and probing electronic transitions in the visible spectral regions. The kinetic results indicate that photoelimination of the CO group occurs on a subpicosecond time scale. The overall quantum yiel…
Excitation energy transfer in isolated chlorosomes from Chloroflexus aurantiacus
Abstract Chlorosomes from green photosynthetic bacteria Chloroflexus aurantiacus have been studied by time-resolved femtosecond transient absorption spectroscopy. The fastest kinetics of 200–300 fs resolved, was interpreted to stem for intra-chlorosomal excitation energy transfer. Energy transfer from the antenna to the baseplate appeared as a major 9.2 ps rise component detected at the baseplate probe wavelength. Excitation energy transfer rates were evaluated for a model chlorosome. Calculated rod to rod, and rods to baseplate rate constants of 200–400 fs and 10–20 ps, respectively, are in accord with the experimental results.
Effects of ligand substitution on the excited state dynamics of the Ru(dcbpy)(CO)2I2 complex
Abstract Spectroscopic evidence suggest [PCCP 3 (2001) 1992] that illumination with visible light of the [trans-I-Ru(dcbpy)(CO)2I2] (dcbpy= 4,4′-dicarboxy-2,2′-bipyridine) complex in solution induces dissociation of a CO group followed by reorganization of the ligands and attachment of a solvent molecule. In the present study, we report results on excited state dynamics of this ruthenium complex and its photoproduct. Femtosecond transient absorption measurements reveal dominance of excited state absorption of the reactant and the photoproduct [cis-I-Ru(dcbpy)(CO)(Sol)I2] (Sol=ethanol or acetonitrile) in the visible spectral region. The time-resolved measurements for the reactant at 77 K ind…