Journal article

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

Abstract

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..

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