Three New Alkaline Beryllium Borates LiBeBO₃, Li₆Be₃B₄O₁₂, and Li₈Be₅B₆O₁₈ in the Ternary Phase Diagrams Li₂O–BeO–B₂O₃

The phase diagram in the Li₂O–BeO–B₂O₃ system has been systematically investigated by the methods of visual polythermal analysis, spontaneous crystallization, and X-ray diffraction. Three new alkaline beryllium borates, namely, LiBeBO₃, Li₆Be₃B₄O₁₂, and Li₈Be₅B₆O₁₈, were synthesized with molten fluxes based on Li₂O–B₂O₃ solvent in this system. All of the materials are centrosymmetric. The similarity of the fundamental building block of the title compounds has been compared. Thermal analysis and powder XRD studies were applied to determine phase relation and their incongruent melting behavior. The UV–vis diffuse reflectance spectroscopy demonstrated that the UV cutoff edges of the aforementioned materials are all below 200 nm

Alkaline-Alkaline Earth Fluoride Carbonate Crystals ABCO₃F (A = K, Rb, Cs; B = Ca, Sr, Ba) as Nonlinear Optical Materials

A new series of alkaline–alkaline earth fluoride carbonates (KSrCO3F, RbSrCO3F, KCaCO3F, RbCaCO3F, CsCaCO3F, and Cs3Ba4(CO3)3F5) were synthesized by spontaneous crystallization with molten fluxes. Their crystal structures, except for Cs3Ba4(CO3)3F5, exhibit the stacking of [AF]∞ (A = K, Rb, Cs) and [B(CO3)]∞ (B = Ca, Sr) layers, and the coplanar alignment of [CO3] triangles. The results from the UV–vis diffuse reflectance spectroscopy study of the powder samples indicated that the short-wavelength absorption edges were all below 200 nm, except for Cs3Ba4(CO3)3F5, which is about 210 nm. Second-harmonic generation (SHG) on polycrystalline samples was measured using the Kurtz and Perry technique, which indicated that these carbonates are all phase-matchable materials in both visible and the UV region, and their measured SHG coefficients were about 3.33, 3.33, 3.61, 1.11, 1.11, and 1.20 times as large as that of d36 (KDP), respectively

Alkaline-Alkaline Earth Fluoride Carbonate Crystals ABCO₃F (A = K, Rb, Cs; B = Ca, Sr, Ba) as Nonlinear Optical Materials

A new series of alkaline–alkaline earth fluoride carbonates (KSrCO₃F, RbSrCO₃F, KCaCO₃F, RbCaCO₃F, CsCaCO₃F, and Cs₃Ba₄(CO₃)₃F₅) were synthesized by spontaneous crystallization with molten fluxes. Their crystal structures, except for Cs₃Ba₄(CO₃)₃F₅, exhibit the stacking of [AF]_∞ (A = K, Rb, Cs) and [B(CO₃)]_∞ (B = Ca, Sr) layers, and the coplanar alignment of [CO₃] triangles. The results from the UV–vis diffuse reflectance spectroscopy study of the powder samples indicated that the short-wavelength absorption edges were all below 200 nm, except for Cs₃Ba₄(CO₃)₃F₅, which is about 210 nm. Second-harmonic generation (SHG) on polycrystalline samples was measured using the Kurtz and Perry technique, which indicated that these carbonates are all phase-matchable materials in both visible and the UV region, and their measured SHG coefficients were about 3.33, 3.33, 3.61, 1.11, 1.11, and 1.20 times as large as that of <i>d</i>₃₆ (KDP), respectively

Na₈Lu₂(CO₃)₆F₂ and Na₃Lu(CO₃)₂F₂: Rare Earth Fluoride Carbonates as Deep-UV Nonlinear Optical Materials

Two nonlinear optical fluoride carbonate crystals (Na₈Lu₂(CO₃)₆F₂ and Na₃Lu­(CO₃)₂F₂) have been synthesized under subcritical hydrothermal condition. Both crystals crystallize in the noncentrosymmetric space group <i>Cc</i> (No. 9). The structure of Na₈Lu₂(CO₃)₆F₂ with high density of [CO₃] groups is described as 1D [Na₅Lu­(CO₃)₂F₂] chains connected by [CO₃] triangles, forming an intricate three-dimensional framework. Lu³⁺ and Na⁺ cations are alternatively ordered and disordered in the cavities of the 3D network. The structure of Na₃Lu­(CO₃)₂F₂ is built up from the [NaLu­(CO₃)₂F₂] layers which are separated by other Na⁺ cations. The [CO₃] anionic groups arrange approximately coparallel to the plane. The second harmonic generation (SHG) measurement indicates that Na₈Lu₂(CO₃)₆F₂ and Na₃Lu­(CO₃)₂F₂ have large SHG responses that are approximately 4.29 and 4.21 times KH₂PO₄ (KDP), respectively. The responses are also phase-matchable in the visible region. In addition, it exhibits wide transparent regions ranging from UV to near IR with a short UV cutoff edge (<200 nm), which suggests that the new compounds are promising as deep-UV NLO materials

Layered Perovskite-like Nitrate Cs₂Pb(NO₃)₂Br₂ as a Multifunctional Optical Material

A novel alkali metal lead halide nitrate, Cs2Pb­(NO3)2Br2, has been successfully synthesized via a hydrothermal method. Interestingly, the title compound features a distinctive Ruddlesden–Popper perovskite-like layered structure, which induces the outstanding multifunctional optical properties, including a large birefringence (0.147@546 nm) and broad light-orange emission. Detailed structural analysis and theoretical calculations revealed that the large birefringence originates from the p−π interaction between the Pb2+ cations and NO3 groups and that the excellent luminescence properties derive from the distortion of PbO4Br4 polyhedra. This work not only enriches the variant structure types of layered perovskites but also guides the further exploration of all-inorganic multifunctional optical materials

Na₈Lu₂(CO₃)₆F₂ and Na₃Lu(CO₃)₂F₂: Rare Earth Fluoride Carbonates as Deep-UV Nonlinear Optical Materials

Two nonlinear optical fluoride carbonate crystals (Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2) have been synthesized under subcritical hydrothermal condition. Both crystals crystallize in the noncentrosymmetric space group Cc (No. 9). The structure of Na8Lu2(CO3)6F2 with high density of [CO3] groups is described as 1D [Na5Lu­(CO3)2F2] chains connected by [CO3] triangles, forming an intricate three-dimensional framework. Lu3+ and Na+ cations are alternatively ordered and disordered in the cavities of the 3D network. The structure of Na3Lu­(CO3)2F2 is built up from the [NaLu­(CO3)2F2] layers which are separated by other Na+ cations. The [CO3] anionic groups arrange approximately coparallel to the plane. The second harmonic generation (SHG) measurement indicates that Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2 have large SHG responses that are approximately 4.29 and 4.21 times KH2PO4 (KDP), respectively. The responses are also phase-matchable in the visible region. In addition, it exhibits wide transparent regions ranging from UV to near IR with a short UV cutoff edge (<200 nm), which suggests that the new compounds are promising as deep-UV NLO materials

Na₈Lu₂(CO₃)₆F₂ and Na₃Lu(CO₃)₂F₂: Rare Earth Fluoride Carbonates as Deep-UV Nonlinear Optical Materials

Two nonlinear optical fluoride carbonate crystals (Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2) have been synthesized under subcritical hydrothermal condition. Both crystals crystallize in the noncentrosymmetric space group Cc (No. 9). The structure of Na8Lu2(CO3)6F2 with high density of [CO3] groups is described as 1D [Na5Lu­(CO3)2F2] chains connected by [CO3] triangles, forming an intricate three-dimensional framework. Lu3+ and Na+ cations are alternatively ordered and disordered in the cavities of the 3D network. The structure of Na3Lu­(CO3)2F2 is built up from the [NaLu­(CO3)2F2] layers which are separated by other Na+ cations. The [CO3] anionic groups arrange approximately coparallel to the plane. The second harmonic generation (SHG) measurement indicates that Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2 have large SHG responses that are approximately 4.29 and 4.21 times KH2PO4 (KDP), respectively. The responses are also phase-matchable in the visible region. In addition, it exhibits wide transparent regions ranging from UV to near IR with a short UV cutoff edge (<200 nm), which suggests that the new compounds are promising as deep-UV NLO materials

Na₈Lu₂(CO₃)₆F₂ and Na₃Lu(CO₃)₂F₂: Rare Earth Fluoride Carbonates as Deep-UV Nonlinear Optical Materials

Two nonlinear optical fluoride carbonate crystals (Na₈Lu₂(CO₃)₆F₂ and Na₃Lu­(CO₃)₂F₂) have been synthesized under subcritical hydrothermal condition. Both crystals crystallize in the noncentrosymmetric space group <i>Cc</i> (No. 9). The structure of Na₈Lu₂(CO₃)₆F₂ with high density of [CO₃] groups is described as 1D [Na₅Lu­(CO₃)₂F₂] chains connected by [CO₃] triangles, forming an intricate three-dimensional framework. Lu³⁺ and Na⁺ cations are alternatively ordered and disordered in the cavities of the 3D network. The structure of Na₃Lu­(CO₃)₂F₂ is built up from the [NaLu­(CO₃)₂F₂] layers which are separated by other Na⁺ cations. The [CO₃] anionic groups arrange approximately coparallel to the plane. The second harmonic generation (SHG) measurement indicates that Na₈Lu₂(CO₃)₆F₂ and Na₃Lu­(CO₃)₂F₂ have large SHG responses that are approximately 4.29 and 4.21 times KH₂PO₄ (KDP), respectively. The responses are also phase-matchable in the visible region. In addition, it exhibits wide transparent regions ranging from UV to near IR with a short UV cutoff edge (<200 nm), which suggests that the new compounds are promising as deep-UV NLO materials

Using Multifunctional Ionic Liquids in the Synthesis of Crystalline Metal Phosphites and Hybrid Framework Solids

Several crystalline metal phosphites and related hybrid framework solids were prepared under ionothermal conditions using ionic liquids as the reactant, templating agent, and solvent. These compounds display different structures and some appealing properties such as proton conduction. A variety of ionic liquids, metal ions, and additional synthetic variants (e.g., F- and organic ligands) can be introduced into the metal phosphite systems, demonstrating the versatility of the synthetic strategy

Na₈Lu₂(CO₃)₆F₂ and Na₃Lu(CO₃)₂F₂: Rare Earth Fluoride Carbonates as Deep-UV Nonlinear Optical Materials

Two nonlinear optical fluoride carbonate crystals (Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2) have been synthesized under subcritical hydrothermal condition. Both crystals crystallize in the noncentrosymmetric space group Cc (No. 9). The structure of Na8Lu2(CO3)6F2 with high density of [CO3] groups is described as 1D [Na5Lu­(CO3)2F2] chains connected by [CO3] triangles, forming an intricate three-dimensional framework. Lu3+ and Na+ cations are alternatively ordered and disordered in the cavities of the 3D network. The structure of Na3Lu­(CO3)2F2 is built up from the [NaLu­(CO3)2F2] layers which are separated by other Na+ cations. The [CO3] anionic groups arrange approximately coparallel to the plane. The second harmonic generation (SHG) measurement indicates that Na8Lu2(CO3)6F2 and Na3Lu­(CO3)2F2 have large SHG responses that are approximately 4.29 and 4.21 times KH2PO4 (KDP), respectively. The responses are also phase-matchable in the visible region. In addition, it exhibits wide transparent regions ranging from UV to near IR with a short UV cutoff edge (<200 nm), which suggests that the new compounds are promising as deep-UV NLO materials