Photogeneration of metastable side-on N-2 linkage isomers in [Ru(NH3)(5)N-2]Cl-2, [Ru(NH3)(5)N-2]Br-2 and [Os(NH3)(5)N-2]Cl-2
Dominik Schaniel, Theo Woike, Bernard Delley, Colette Boskovic, Hans-Ueli Guedel
PHYSICAL CHEMISTRY CHEMICAL PHYSICS | ROYAL SOC CHEMISTRY | Published : 2008
Photogeneration of side-on N2 linkage isomers in [Ru(NH3)5N2]2+ and [Os(NH3)5N2]2+ is achieved by irradiation with lambda = 325 nm of powder samples at T = 80 K and detected by the downshift of the nu(N-N) vibration and by the heat release at elevated temperature due to the back switching of the side-on configuration to the ground state. The concentration of the transferred molecules is evaluated by the decrease of the area of the nu(N-N) or 2nu(N-N) vibrational bands. All characteristic changes between the linear Ru-N-N and side-on configuration are predicted by DFT calculations: the structure of the anion, shifts of the vibrations, electronic excitation energy, energetic position and seque..View full abstract
Awarded by the Deutsche Forschungsgemeinschaft
Awarded by the BMBF
Financial support by the Swiss National Science Foundation, the Deutsche Forschungsgemeinschaft (WO618/8-1, SCHA1550/1-1) and the BMBF (FKZ 03X5510) is gratefully acknowledged.