Electronic spectra of the hexahalo anions of osmium(IV) and iridium(IV)

Theoretical study of the effects of F to Cl chemical substitution on the electronic structure and the luminescence properties of Cs2GeF6:Os4+ and Cs2ZrCl6:Os4+ materials

“…No definite determination of the transition energy to the ͑ 5 E g ͒ states has been provided, although values ranging from 16 000 to 21000 cm −1 have been suggested in the literature from estimations. 9,11,13,18 In a specific search for this state, Kozikowsky and Kiederling 18 did not find any hint of it lying lower than 20 400 cm −1 . In this point we would like to pay some attention to a broad band, centered around 22 000 cm −1 , reported from absorption spectra.…”

“…The optical spectrum and magnetic circular dichroism spectrum of Os 4+ :Cs 2 ZrCl 6 have been studied in the past [8][9][10][11] and the ͑OsCl 6 ͒ 2− chromophore has been studied in other lattices as well [12][13][14][15][16][17][18] and in solution, 19,20 but the studies on the spectrum of ͑OsF 6 ͒ 2− are less numerous. 7,13,21 Both Cs 2 GeF 6 and Cs 2 ZrCl 6 are cubic crystals, with the potassium chloroplatinate structure 22 and the dopant Os 4+ ion which substitutes for a tetravalent cation ͑Ge 4+ or Zr 4+ ͒, in a perfect octahedral coordination. Free Os 4+ has the 5d 4 electronic structure and in octahedral coordination, even in halide compounds, promotes a large ligand field splitting, so that the 3 T 1g ͑t 2g 4 ͒ state becomes the ground state, being followed in energy by predominantly spin singlet t 2g 4 levels.…”

Synthesis and Characterization of Barium Hexafluoridoosmates

“…The fluoroanions of osmium, OsF 6 − and OsF 6 2− , are known since the 1950s. The first compounds containing these species were prepared by Hepworth and coworkers [1]: MOsF 6 (M = Li, K, Rb, Cs, Ag) and M 2 OsF 6 (M = K, Cs), and were later characterized by various techniques, such as IR spectroscopy [2][3][4][5][6] and X-ray diffraction [7][8][9].…”

“…The first compounds containing these species were prepared by Hepworth and coworkers [1]: MOsF 6 (M = Li, K, Rb, Cs, Ag) and M 2 OsF 6 (M = K, Cs), and were later characterized by various techniques, such as IR spectroscopy [2][3][4][5][6] and X-ray diffraction [7][8][9]. Both anions can be of relevance for the urban mining processes [10,11] and the analytical chemistry of osmium [12,13].…”

“…Here, we present our results on the syntheses and characterization of the two barium hexafluoridoosmates: BaOsF 6 and Ba(OsF 6 ) 2 . Also, we briefly report three derivatives of barium hexafluoridoosmate(V), which are solvates: "Ba(OsF 6 ) 2 ·nBrF 3 ", "Ba(OsF 6 ) 2 ·nHF", and Ba(OsF 6 ) 2 ·6H 2 O.…”