A series of pentanary inorganic supramolecular sulfides (A3X)[MB12(MS4)3] (A = K, Cs; X = Cl, Br, I; M = Ga, In, Gd) featuring B12S12 clusters

A series of new pentanary inorganic supramolecular sulfides (A(3)X)[MB12(MS4)(3)] (A = K, Cs; X = Cl, Br, I; M = Ga, In, Gd) have been synthesized using high-temperature solid-state reactions. They crystallize in the noncentrosymmetric hexagonal space group P6(3)22. Their structures feature a MS4 tetrahedra saturated B-12 icosahedron, and the latter is also alternately connected with a MS6 octahedron via face sharing to form a chain. [(A(3)X)(2+)](n) polycationic chains fill in the 1D channels of the 3D open-framework {[MB12(MS4)3](2-)}(n). A discussion about their structural chemistry is also presented. Their second-order nonlinear optical (NLO) properties are calculated using Material Studio software, and the results show that this series of thioborates show tunable NLO properties.