Noncentrosymmetric Ba₆In₂Q₁₀ (Q = S, Se): Structural Chemistry and Nonlinear-Optical Activity

The indispensable condition for laser frequency-doubling crystal materials is that they crystallize in the noncentrosymmetric (NCS) structures. Here, ternary NCS Ba₆In₂S₁₀ (1) and Ba₆In₂Se₁₀ (2) (P6₃) were synthesized via conventional solid-state reactions. Their zero-dimensional structures feature isolated InQ₄ tetrahedra and Q₂^2– (Q = S, Se) dimers that are separated by Ba²⁺ counter cations. The structural relevance and differences with the centrosymmetric Ba₁₂In₄S₁₉ and Ba₁₂In₄Se₂₀ are analyzed in detail. Both 1 and 2 show obvious laser frequency-doubling activity, and their optical band gaps are 3.72 and 1.78 eV, respectively. This work provides a new type of IR nonlinear-optical materials.