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Photochemical reaction of sulfur hexafluoride with water in low-temperature xenon matrices.

Sulfur hexafluoride SF(6) is a very stable molecule with which very few reactions with other molecules have been reported. Here, we report a photochemical reaction of SF(6) with water molecules using a matrix-isolation technique, where SF(6) and H(2)O were co-condensed in Xe matrices, and the products were observed using infrared spectroscopy. Irradiation at 193 nm from an ArF excimer laser caused the simultaneous decomposition of SF(6) and H(2)O, which resulted in the production of novel species. Infrared spectra and molecular orbital calculations of the species showed that the product was a SF(4)⋯HF⋯HOF complex, which consists of hydrogen bonds and charge transfer interaction between S and F atoms. The assignment of the species was confirmed by isotope shifts using D and (18)O isotope substitutions.