- Crystal structures and pressure-induced redox reaction of Cs2PdI4·I2 to Cs2PdI6
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Two iodopalladates of the same empirical formula with palladium in different oxidation states were synthesized from aqueous HI solution. Their crystal structures were characterized by single-crystal X-ray analysis, and the effect of hydrostatic pressure on the structural properties has been investigated. Dicesium hexaiodopalladate(IV), Cs2PdI6, crystallizes in a cubic system, space group Fm3m, with a = 11.332(1) A and Z = 4, and is isotypic to K2PtCl6. The second compound, dicesium tetraiodopalladate(II) diiodine, Cs2PdI4·I2, shows tetragonal symmetry with space group I4/mmm, a = 8.987(1) A, c = 9.240(1) A, and Z = 2. The crystal structure can be described in resemblance to the Cs2Au(I)Au(III)Cl6 type. Structural relationships and chemical and structural transformation between both compounds will be discussed. DTA measurements at ambient pressure showed liberation of I2 and decomposition of the compounds. Cs2PdI4·I2 represents an excellent example for studying a solid-state electron-transfer reaction. The redox reaction to Cs2PdI6 can be demonstrated by performing pressure-dependent X-ray studies.
- Schuepp,Heines,Savin,Keller
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- Resonance Raman and ultraviolet absorption spectra of the triiodide ion produced by alkali iodide-iodine argon matrix reactions
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Matrix reactions of alkali iodide and iodine molecules were performed to produce the M+I3- species for spectroscopic comparison to triiodide ion solution data. Strong ultraviolet absorptions at 287 and 355 nm and a strong resonance Raman fundamental at 113 ± 1 cm-1 with five overtones are in excellent agreement with previous solution spectra. The salt-molecule reaction technique produces new M+X3- species, which are clearly representative of the polyhalide ion itself.
- Andrews, Lester,Prochaska, Eleanor S.,Loewenschuss, Aharon
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- Electronic Spectra and Structures of Polyiodide Chain Complexes
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Electronic spectra and electronic structures of triiodide, pentaiodide, and polyiodide chain complexes are investigated by electronic and Raman spectral measurements on nine single crystals of complexes with theoretical considerations.The assignments of o
- Mizuno, Masagi,Tanaka, Jiro,Harada, Issei
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- Behavior of I2 and J3- Molecular Units Near the Crystal Surface of CsI and Related Polyiodides. Raman-Spectroscopic Studies
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Raman spectra of CsI3 and Cs2I8 crystals were measured for the samples whose structures were carefully examined.The surface of Cs2I8 samples was found to turn into CsI3 when they were kept in air.The heating effect of laser irradiation was shown to change
- Odagi, Kazumasa,Nakayama, Hideyuki,Ishi, Kikujiro
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- Well-ordered crystals of TaI5. The formation of the ternary iodide CsTaI6
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Well ordered single crystals of TaI5 (orthorhombic, Pnma (no. 62), a = 1396.2(2), b = 2009.5(4), c = 660.7(1) pm, Z = 8, R1 for 967 reflections with I02σ(I0): 0.0381) were obtained from a reaction of the elements. The structure determination confirms Mueller's prediction of 1978. Single crystals of CsTaI6 (monoclinic, C2/c (no. 15), a = 1362.3(2), b = 709.9(1), c = 1736.2(3) pm, β = 128.77(1)° , Z = 4, R1 for 1140 reflections with I 02σ(I0): 0.0378) were obtained by the oxidation of tantalum with CsI3. Both crystal structures contain [TaI6] octahedra which are edge-connected to Ta2I10 dimers in TaI5 and isolated as [TaI6]- anions in the salt Cs[TaI6] (CsWCl6 type of structure).
- Habermehl, Katja,Pantenburg, Ingo,Held, Peter,Meyer, Gerd
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p. 829 - 831
(2009/04/13)
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