Synthesis, Ion Exchange, and Nonlinear Optical Properties of Different Dimension Chalcogenidostannates Driven by StructureDirecting Agents

Chalcogenidostannates possess diverse properties that are promising for various applications. Under solvothermal conditions, we synthesized two new compounds: Rb6Cd4Sn3Se13 (1) and [Eu(trien)(tren)Cl]Hg2SnSe5 (2) (trien = triethylenetetramine; tren = tris(2-aminoethyl)amine). Compound 1 features a 3D anionic framework with Rb+ cations containing a large 18-membered ring. Compound 2 exhibits a double-chain anionic structure separated by the [Eu(trien)(tren)Cl]n2n+ complexes. Both Rb+ and the lanthanide complex act as distinct structure-directing agents, significantly influencing the final architectures. Both compounds demonstrate excellent photocurrent responses (ca. 12.6 μA/cm2 for 1; ca. 129.3 μA/cm2 for 2) and were evaluated for photocatalytic methylene blue (MB) degradation. Theoretical calculations elucidated the optical-electronic structure relationships. Crucially, 1 exhibits superior Cs+/Sr2+ ion-exchange capability and a powder second-harmonic generation (SHG) response ∼0.38 times that of AgGaSe2 (150-200 μm particles).