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The new compounds Li2Mg2Si2S6 and Li2Mg2Ge2S6 have been prepared via traditional high‐temperature, solid‐state synthesis. The title compounds crystallize in the polar, noncentrosymmetric, trigonal space group P31m (No. 157) and adopt a new structure type featuring staggered, ethane‐like (T2S6)6− units, where T=Si or Ge. These (T2S6)6− units are nestled within the holes of magnesium‐sulfide "layers" that are created through the edge‐sharing of MgS6 octahedra. The holes found in the lithium‐sulfide "layers", created by LiS6 edge‐sharing octahedra, remain vacant, containing no (T2S6)6− anionic group. Through the face sharing of the respective MgS6 and LiS6 octahedra, the magnesium‐sulfide and lithium‐sulfide "layers" are stitched together resulting in an overall three‐dimensional structure. The optical bandgaps of Li2Mg2Si2S6 and Li2Mg2Ge2S6 are 3.24 and 3.18 eV, respectively, as estimated from optical diffuse reflectance UV‐Vis‐NIR spectroscopy. The compounds exhibit second harmonic generation responses of ∼0.24×KDP and ∼2.92×α‐quartz for Li2Mg2Si2S6 and ∼0.17×KDP and ∼2.08×α‐quartz for Li2Mg2Ge2S6, using a Nd:YAG laser at 1.064 μm. Electronic structure calculations were performed using density functional theory and the linearized augmented plane‐wave approach within the WIEN2k software package. Examination of the electronic band structures shows that these compounds are indirect bandgap semiconductors. [ABSTRACT FROM AUTHOR]

The new, quaternary diamond-like semiconductor (DLS) Cu4MnGe2S7 was prepared at high-temperature from a stoichiometric reaction of the elements under vacuum. Single crystal X-ray diffraction data were used to solve and refine the structure in the polar space group Cc. Cu4MnGe2S7 features [Ge2S7]6− units and adopts the Cu5Si2S7 structure type that can be considered a derivative of the hexagonal diamond structure. The DLS Cu2MnGeS4 with the wurtz-stannite structure was similarly prepared at a lower temperature. The achievement of relatively phase-pure samples, confirmed by X-ray powder diffraction data, was nontrival as differential thermal analysis shows an incongruent melting behaviour for both compounds at relatively high temperature. The dark red Cu2MnGeS4 and Cu4MnGe2S7 compounds exhibit direct optical bandgaps of 2.21 and 1.98 eV, respectively. The infrared (IR) spectra indicate potentially wide windows of optical transparency up to 25 μm for both materials. Using the Kurtz–Perry powder method, the second-order nonlinear optical susceptibility, χ(2), values for Cu2MnGeS4 and Cu4MnGe2S7 were estimated to be 16.9 ± 2.0 pm V−1 and 2.33 ± 0.86 pm V−1, respectively, by comparing with an optical-quality standard reference material, AgGaSe2 (AGSe). Cu2MnGeS4 was found to be phase matchable at λ = 3100 nm, whereas Cu4MnGe2S7 was determined to be non-phase matchable at λ = 1600 nm. The weak SHG response of Cu4MnGe2S7 precluded phase-matching studies at longer wavelengths. The laser-induced damage threshold (LIDT) for Cu2MnGeS4 was estimated to be ∼0.1 GW cm−2 at λ = 1064 nm (pulse width: τ = 30 ps), while the LIDT for Cu4MnGe2S7 could not be ascertained due to its weak response. The significant variance in NLO properties can be reasoned using the results from electronic structure calculations. [ABSTRACT FROM AUTHOR]

The stability of hot aqueous solutions of ammonium nitrate have been investigated in an attempt to determine various mechanisms of nitrous oxide formation. Hot aqueous NHsub3 and HNOsub3 were combined in a titanium sparger, and the neutralization reaction may lead to temperatures of 180 degrees C. Low pH is often used to suppress reaction during NHsub4Nosub3 synthesis.

Reductive carbonylation of TaCl5 in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) under the proper conditions produces TaCl(CO)2(dppe)2 (1) and the possibly cyclic oligomer (TaCl(CO)2(dppe)2)2x (2, 2x >/= 4). Carbonylation of 1 results in the rapid but reversible formation of TaCl(CO)4(dppe) (3). Solutions of all three compounds show low levels of paramagnetism.

Highlights: [•] The title compounds were prepared by a high-temperature, direct-combination route. [•] The room temperature structure of Li4SnS4 is reported in space group Pnma. [•] The Li(2)S4 tetrahedra invert upon going from the RT to low temperature structure. [•] Electronic structure calculations indicate the Li–S bonding to be primarily ionic. [•] Li4GeS4 and Li4SnS4 have shown to be stable up to ∼850 and 950°C respectively. [ABSTRACT FROM AUTHOR]

The new, quaternary diamond-like semiconductor (DLS) Cu 4 MnGe 2 S 7 was prepared at high-temperature from a stoichiometric reaction of the elements under vacuum. Single crystal X-ray diffraction data were used to solve and refine the structure in the polar space group Cc. Cu 4 MnGe 2 S 7 features [Ge 2 S 7 ] 6- units and adopts the Cu 5 Si 2 S 7 structure type that can be considered a derivative of the hexagonal diamond structure. The DLS Cu 2 MnGeS 4 with the wurtz-stannite structure was similarly prepared at a lower temperature. The achievement of relatively phase-pure samples, confirmed by X-ray powder diffraction data, was nontrival as differential thermal analysis shows an incongruent melting behaviour for both compounds at relatively high temperature. The dark red Cu 2 MnGeS 4 and Cu 4 MnGe 2 S 7 compounds exhibit direct optical bandgaps of 2.21 and 1.98 eV, respectively. The infrared (IR) spectra indicate potentially wide windows of optical transparency up to 25 μm for both materials. Using the Kurtz-Perry powder method, the second-order nonlinear optical susceptibility, χ (2) , values for Cu 2 MnGeS 4 and Cu 4 MnGe 2 S 7 were estimated to be 16.9 ± 2.0 pm V -1 and 2.33 ± 0.86 pm V -1 , respectively, by comparing with an optical-quality standard reference material, AgGaSe 2 (AGSe). Cu 2 MnGeS 4 was found to be phase matchable at λ = 3100 nm, whereas Cu 4 MnGe 2 S 7 was determined to be non-phase matchable at λ = 1600 nm. The weak SHG response of Cu 4 MnGe 2 S 7 precluded phase-matching studies at longer wavelengths. The laser-induced damage threshold (LIDT) for Cu 2 MnGeS 4 was estimated to be ∼0.1 GW cm -2 at λ = 1064 nm (pulse width: τ = 30 ps), while the LIDT for Cu 4 MnGe 2 S 7 could not be ascertained due to its weak response. The significant variance in NLO properties can be reasoned using the results from electronic structure calculations.