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Issue 37, 2007
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Generation of one light-induced metastable nitrosyl linkage isomer in [Pt(NH3)4Cl(NO)]Cl2 in the red spectral range

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Abstract

One metastable linkage nitrosyl isomer can be generated in [Pt(NH3)4Cl(NO)]Cl2 by irradiation with light in the red spectral range. The potential energy barrier for the thermal relaxation of the metastable state to the ground state has an amount of EA = (0.27 ± 0.03) eV. The decay follows the Arrhenius law and EA is independent of temperature. At room temperature the metastable state has a lifetime of τ = 3.8 × 10−5 s after generation by pulsed laser illumination. Below T = 100 K about 30% linkage NO isomers can be generated in a powder sample by irradiation with λ = 658 nm. DFT calculations demonstrate the rotation of the NO ligand from Pt–N–O to Pt–O–N as a unique linkage isomer. Consequently, only one new ν(NO) stretching vibration is detected with a shift from 1673 cm−1 to 1793 cm−1 by 120 cm−1, to higher frequencies in good agreement with the DFT calculations. In the metastable state new electronic absorption bands are observed in the blue-green and near infrared spectral range. The metastable state can be optically accessed via a (5d + π(NO)) → π*(NO) transition. [Pt(NH3)4Cl(NO)]Cl2 is diamagnetic with a Pt(5d8) configuration and thus represents the first {MNO}8 complex with experimental evidence for a light-induced nitrosyl linkage isomer.

Graphical abstract: Generation of one light-induced metastable nitrosyl linkage isomer in [Pt(NH3)4Cl(NO)]Cl2 in the red spectral range

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Publication details

The article was received on 24 May 2007, accepted on 09 Jul 2007 and first published on 25 Jul 2007


Article type: Paper
DOI: 10.1039/B707912E
Citation: Phys. Chem. Chem. Phys., 2007,9, 5149-5157
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    Generation of one light-induced metastable nitrosyl linkage isomer in [Pt(NH3)4Cl(NO)]Cl2 in the red spectral range

    D. Schaniel, T. Woike, B. Delley, D. Biner, K. W. Krämer and H. Güdel, Phys. Chem. Chem. Phys., 2007, 9, 5149
    DOI: 10.1039/B707912E

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