NaMn3Ga3S8: Noncentrosymmetric inorganic metal chalcogenide with nonlinear optical response, antiferromagnetic, and photoluminescence performances

Inorganic chalcogenides capable of exhibiting many interesting functional properties, e.g. nonlinear optics, magnetism , luminescence, catalysis, have attracted considerable attention, yet coupling these properties in one compound to construct a new multifunctional chalcogenide is still rarely reported. Herein, we synthesized a novel noncentrosymmetric metal chalcogenide, NaMn 3 Ga 3 S 8 by the traditional high-temperature solid-state reaction, which can exhibit three interesting functional properties, including nonlinear optical (NLO) response, photoluminescence , and antiferromagnetism simultaneously. The single-crystal X-ray diffraction shows it crystallizes in the hexagonal space group P-6, with unit cell parameters a = 16.787 (8), c = 3.707 (3), Z = 3. In the structure, MnS 6 octahedra form a chain-like configuration that is interconnected with GaS 4 tetrahedra through vertex-, edge-sharing to construct a three-dimensional framework with the Na cations residing in the cavities. Experiments demonstrate that NaMn 3 Ga 3 S 8 shows a large second harmonic generation response at 2.09 μm about 1.6 times that of the benchmark AgGaS 2 with valuable phase-matchable features. Meanwhile, NaMn 3 Ga 3 S 8 can also exhibit antiferromagnetic characteristics with a Néel temperature of 8.6 K and luminescence emissions around 776 nm. Besides, to further analyze the structure−properties relationship, the source of multifunctional properties of the target compound is analyzed by first-principles calculation. These suggest that rational selection of structural components will be a viable approach for designing and discovering novel multifunctional metal chalcogenides .