Search for: All records

Transient absorption data of [Fe II (tpy)(CN) 3 ] − reveals spectroscopic signatures indicative of 3 MLCT with a ∼10 ps kinetic component. These data are supported by DFT and TD-DFT calculations, which show that excited state ordering is responsive to the number of cyanide ligands on the complex. 

We report the excited-state behavior of a structurally simple bis -sulfoxide complex, cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ , as investigated by femtosecond pump–probe spectroscopy. The results reveal that a single photon prompts phototriggered isomerization of one or both dmso ligands to yield a mixture of cis -S,O-[Ru(bpy) 2 (dmso) 2 ] 2+ and cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . The quantum yields of isomerization of each product and relative product distribution are dependent upon the excitation wavelength, with longer wavelengths favoring the double isomerization product, cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ . Transient absorption measurements on cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ do not reveal an excited-state isomerization pathway to produce either the S,O or S,S isomers. Femtosecond pulse shaping experiments reveal no change in the product distribution. Pump–repump–probe transient absorption spectroscopy of cis -S,S-[Ru(bpy) 2 (dmso) 2 ] 2+ shows that a pump–repump time delay of 3 ps dramatically alters the S,O : O,O product ratio; pump–repump–probe transient absorption spectroscopy of cis -O,O-[Ru(bpy) 2 (dmso) 2 ] 2+ with a time delay of 3 ps uncovers an excited-state isomerization pathway to produce the S,O isomer. In conjunction with low-temperature steady-state emission spectroscopy, these results are interpreted in the context of an excited-state bifurcating pathway, in which the isomerization product distribution is determined not by thermodynamics, but rather as a dynamics driven reaction. 

A new pyridine-bis(carboxamide)-based ligand with a bithiophene pendant, 2Tcbx, was synthesized. Its lanthanide ion (Ln III ) complexes, [Ln(2Tcbx) 2 ] 3+ , were isolated and their photophysical properties were explored. Upon excitation at 360 nm, these complexes display emission in the near-infrared (NIR) with efficiencies of 0.69% for Ln III = Yb III , 0.20% for Ln III = Nd III , and 0.01% for Ln III = Er III , respectively. Concurrent 1 O 2 formation was seen for all complexes, with efficiencies of 19% for the Yb III complex, 25% for the Nd III complex, and 9% for the Er III complex. When exciting at a longer wavelength, 435 nm, only Ln III emission was observed and larger efficiencies of Ln III -centered emission were obtained. The lack of 1 O 2 generation indicates that energy pathways involving different ligand conformations, which were investigated by transient absorption spectroscopy, are involved in the sensitization process, and enable the wavelength-dependent generation of 1 O 2 .