Second-harmonic-generation of [(Se,Te)Cl$_{3}$]$^{+}$ [GaCl$_{4}$]$^{–}$ with aligned ionic tetrahedra

[SeCl$_{3}$][GaCl$_{4}$] (1) and [TeCl$_{3}$][GaCl$_{4}$] (2) are prepared via Lewis-acid–base reaction of SeCl$_{4}$ or TeCl$_{4}$ with GaCl$_{3}$ at 50 °C (1) and 140 °C (2) in quantitative yield. The ionic compounds contain pseudo-tetrahedral [SeCl$_{3}$]$^{+}$/[TeCl$_{3}$]$^{+}$ cations with a prominent stereochemically active electron lone pair at Se(IV)/Te(IV) as well as tetrahedral [GaCl$_{4}$]$^{–}$ anions. Both compounds crystallize in the polar chiral space group P1 with an unidirectional alignment of all tetrahedral building units. They can be considered as the first examples of a much larger group of ionic compounds [MX$_{3}$]$^{+}$[M′X$_{4}$]$^{–}$ (M, M′: metal or main-group element, X: halogen) showing nonlinear optical effects. Material characterization is performed by X-ray structure analysis based on single crystals and powder samples, thermogravimetry, optical spectroscopy, infrared and Raman spectroscopy. Second harmonic generation (SHG) is observed with intensities about 3-times stronger than for potassium dihydrogen phosphate (KDP) in the visible spectral regime with narrow-band-gap materials (2.8, 3.2 eV). Density functional theory calculations are employed to complement the experimental findings, interpret the Raman spectra, visualize the stereochemically active lone electron pair, and compute the SHG tensor.