Abstract
The solid state photolysis of (Bu4N)2[Pt(NO3)6] salt, accompanied by sharp changing of the colour from light-yellow to brown and green is investigated by a combination of techniques such as electronic paramagnetic resonance, infrared spectroscopy, Raman spectroscopy, and diffuse reflectance spectroscopy. A paramagnetic Pt(III) complex [Pt(NO3)5] 2− is shown to be a product of photolysis at 455 nm and shorter wavelength sources generated due to reduction of Pt(IV) centres with the elimination of the reactive nitrate-radical. Prolonged irradiation or aging in the dark results in the formation of mixed-valence Pt(III)-Pt(IV) species from trapped [Pt(NO3)5] 2− and [Pt(NO3)6]2− anions of the host structure. The obtained experimental results are supplemented and compared with the data of density functional theory (DFT) calculations, which allows suggesting a possible mechanism of the studied process.
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