K₂Pb₃(CO₃)₃F₂ and KCdCO₃F: Novel Fluoride Carbonates with Layered and 3D Framework Structures

Abstract

Two new mixed metal fluoride carbonates, KCdCO3F and K2Pb3(CO3)3F2, have been synthesized by solvothermal and solid-state techniques. KCdCO3F crystallizes in the acentric nonpolar space group P6̅m2, and its structure features a three-dimensional anionic framework in which the CdCO3 layers are further interconnected by bridging F(-) anions with the negative charge balanced by K(+) cations. K2Pb3(CO3)3F2 crystallizes in the centrosymmetric space group P63/mmc, and its structure exhibits a layered anionic skeleton featuring corner-shared PbO6F and PbO6F2 polyhedra. UV-vis diffuse reflectance spectroscopy studies show that the short-wavelength absorption edges of KCdCO3F and K2Pb3(CO3)3F2 are 227 and 287 nm, respectively. The second harmonic generation (SHG) measurement reveals that KCdCO3F is a phase-matchable material for generation of doubled-frequency light at both 532 and 266 nm, with a large SHG response of approximately 5.2 times that of KH2PO4 (KDP) at 532 nm and a moderate SHG response of approximately 0.75 times that of β-BaB2O4 (BBO) at 266 nm. Therefore, it is a promising UV material for fourth harmonic generation on a 1064 nm Q-switched Nd:YAG laser.