Daniel Friedrich

Synthesis, structural characterization, and physical properties of Cs2Ga2S5, and redetermination of the crystal structure of Cs2S6.

The reaction of CsN3 with GaS and S at elevated temperatures results in Cs2Ga2S5. Its crystal structure was determined from single-crystal X-ray diffraction data. The colorless solid crystallizes in space group C2/c (no. 15) with V = 1073.3(4) Å(3) and Z = 4. Cs2Ga2S5 is the first compound that features one-dimensional chains ∞(1)([Ga2S3(S2)(2-)] of edge- and corner-sharing GaS4 tetrahedra. The vibrational band of the S2(2-) units at 493 cm(-1) was revealed by Raman spectroscopy. Cs2Ga2S5 has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN3 yields elemental Cs, which reacts with sulfur to provide Cs2S6 as an intermediate product. The crystal structure of Cs2S6 was redetermined from selected single crystals. The red compound crystallizes in space group P1 with V = 488.99(8) Å(3) and Z = 2. Cs2S6 consists of S6(2-) polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs2Ga2S5 are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas Ga-S and S-S form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S2 units.

Polymorphism of CsGaS2 – structural characterization of a new two-dimensional polymorph and study of the phase-transition kinetics

CsGaS2-mC64 was obtained by reaction of CsN3 with stoichiometric amounts of Ga2S3 and S at elevated temperatures. The crystal structure of the air- and moisture stable compound was determined from single-crystal X-ray diffraction data. The colourless solid crystallizes in the monoclinic space group C2/c (no. 15) with the lattice parameters a = 10.5718(6) A, b = 10.5708(6) A, c = 16.0847(8) A, β = 99.445(4)°, V = 1773.1(2) A3, and Z = 16. The compound crystallizes in the TlGaSe2 structure type and features anionic layers 2∞[Ga4S84−] consisting of corner-sharing Ga4S10 supertetrahedra. At temperatures above 600 °C an irreversible phase-transition to CsGaS2-mC16 occurs. The phase-transition kinetics were studied using in situ high-temperature X-ray powder diffraction techniques. This transition can only be reversed by using high pressures (>5 GPa at 500 °C). The compound was further characterized using Raman- and diffuse reflectance spectroscopy. Chemical bonding was analysed by DFT calculations.

In Situ X-ray Diffraction Study of the Thermal Decomposition of Selenogallates Cs2[Ga2(Se2)2–xSe2+x] (x = 0, 1, 2)

The selenogallates CsGaSe3 and Cs2Ga2Se5 release gaseous selenium upon heating. An in situ high-temperature X-ray powder diffraction analysis revealed a two-step degradation process from CsGaSe3 to Cs2Ga2Se5 and finally to CsGaSe2. During each step, one Se22- unit of the anionic chains in Cs2[Ga2(Se2)2- xSe2+ x] ( x = 0, 1, 2) decomposes, and one equivalent of selenium is released. This thermal decomposition can be reverted by simple addition of elemental selenium and subsequent annealing of the samples below the decomposition temperature. The influence of the diselenide units in the anionic selenogallate chains on the optical properties and electronic structures was further studied by UV/vis diffuse reflectance spectroscopy and relativistic density functional theory calculations, revealing increasing optical band gaps with decreasing Se22- content.