Issue 37, 2007

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

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

Supplementary files

Article information

Article type
Paper
Submitted
24 May 2007
Accepted
09 Jul 2007
First published
25 Jul 2007

Phys. Chem. Chem. Phys., 2007,9, 5149-5157

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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