Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH 3)5N2]Br2 and [Os(NH 3)5N2]Cl2

Abstract

Photogeneration of side-on N2 linkage isomers in [Ru(NH 3)5N2]2+ and [Os(NH 3)5N2]2+ is achieved by irradiation with λ = 325 nm of powder samples at T = 80 K and detected by the downshift of the ν(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 ν(N-N) or 2ν(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 sequence of..