Crystal structure, electronic structure, and optical properties of the novel Li4CdGe2S7, a wide‐bandgap quaternary sulfide with a polar structure derived from lonsdaleite

The novel quaternary thiogermanate Li4CdGe2S7 (tetralithium cadmium digermanium heptasulfide) was discovered from a solid‐state reaction at 750 °C. Single‐crystal X‐ray diffraction data were collected and used to solve and refine the structure. Li4CdGe2S7 is a member of the small, but growing, class of I4–II–IV2–VI7 diamond‐like materials. The compound adopts the Cu5Si2S7 structure type, which is a derivative of lonsdaleite. Crystallizing in the polar space group Cc, Li4CdGe2S7 contains 14 crystallographically unique ions, all residing on general positions. Like all diamond‐like structures, the compound is built of corner‐sharing tetrahedral units that create a relatively dense three‐dimensional assembly. The title compound is the major phase of the reaction product, as evidenced by powder X‐ray diffraction and optical diffuse reflectance spectroscopy. While the compound exhibits a second‐harmonic generation (SHG) response comparable to that of the AgGaS2 (AGS) reference material in the IR region, its laser‐induced damage threshold (LIDT) is over an order of magnitude greater than AGS for λ = 1.064 µm and τ = 30 ps. Bond valence sums, global instability index, minimum bounding ellipsoid (MBE) analysis, and electronic structure calculations using density functional theory (DFT) were used to further evaluate the crystal structure and electronic structure of the compound and provide a comparison with the analogous I2–II–IV–VI4 diamond‐like compound Li2CdGeS4. Li4CdGe2S7 appears to be a better IR nonlinear optical (NLO) candidate than Li2CdGeS4 and one of the most promising contenders to date. The exceptional LIDT is likely due, at least in part, to the wider optical bandgap of ∼3.6 eV. The novel quaternary thiogermanate Li4CdGe2S7 was discovered from a solid‐state reaction at 750 °C. The compound adopts the Cu5Si2S7 structure type, which is a derivative of lonsdaleite. Li4CdGe2S7 appears to be a better IR nonlinear optical candidate than Li2CdGeS4 and one of the most promising contenders to date.