Issue 9, 2023

Second-harmonic-generation of [(Se,Te)Cl3]+[GaCl4] with aligned ionic tetrahedra

Abstract

[SeCl3][GaCl4] (1) and [TeCl3][GaCl4] (2) are prepared via Lewis-acid–base reaction of SeCl4 or TeCl4 with GaCl3 at 50 °C (1) and 140 °C (2) in quantitative yield. The ionic compounds contain pseudo-tetrahedral [SeCl3]+/[TeCl3]+ cations with a prominent stereochemically active electron lone pair at Se(IV)/Te(IV) as well as tetrahedral [GaCl4] 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 [MX3]+[MX4] (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.

Graphical abstract: Second-harmonic-generation of [(Se,Te)Cl3]+[GaCl4]− with aligned ionic tetrahedra

Supplementary files

Article information

Article type
Research Article
Submitted
16 Dec 2022
Accepted
13 Mar 2023
First published
30 Mar 2023
This article is Open Access
Creative Commons BY license

Inorg. Chem. Front., 2023,10, 2636-2644

Second-harmonic-generation of [(Se,Te)Cl3]+[GaCl4] with aligned ionic tetrahedra

M. A. Bonnin, L. Bayarjargal, V. Milman, B. Winkler and C. Feldmann, Inorg. Chem. Front., 2023, 10, 2636 DOI: 10.1039/D2QI02677E

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