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Issue 36, 2008
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Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH3)5N2]Br2 and [Os(NH3)5N2]Cl2

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Abstract

Photogeneration of side-on N2 linkage isomers in [Ru(NH3)5N2]2+ and [Os(NH3)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 the electronic orbitals, the potentials of the ground and relaxed metastable state with the activation energy, saddle points and energetic position of the minimum.

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

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Publication details

The article was received on 24 Apr 2008, accepted on 09 Jun 2008 and first published on 23 Jul 2008


Article type: Paper
DOI: 10.1039/B806933F
Citation: Phys. Chem. Chem. Phys., 2008,10, 5531-5538
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    Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH3)5N2]Br2 and [Os(NH3)5N2]Cl2

    D. Schaniel, T. Woike, B. Delley, C. Boskovic and H. Güdel, Phys. Chem. Chem. Phys., 2008, 10, 5531
    DOI: 10.1039/B806933F

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