Syntheses, structural characterization, and nonlinear optical properties of mixed alkaline/alkaline earth metal borophosphates

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-08-19 DOI:10.1016/j.jssc.2025.125575

Yang Pan , Jian Deng , Yucheng Hao , Xi Zhao , Yuanyuan Bao , Zixuan Fang , Chonghai Deng , Kunhong Hu , Wei Cheng , Yuan Lin

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Abstract

Borophosphates have attracted significant attention due to their unique structural characteristics and exceptional properties. The incorporation of monovalent alkaline metals and divalent alkaline earth metals into the borophosphate system has significantly diversified the crystal structures. A new borophosphate, KMg [B(PO₄)₂](H₂O)₂, along with two previously reported nonlinear optical (NLO) materials, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O), were synthesized using low-temperature hydrothermal methods. These compounds crystallized in the same polar space group of P6₁22. The fundamental building units of KMg [B(PO₄)₂](H₂O)₂, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O) consist of BO₄ tetrahedra, PO₄ tetrahedra and MgO₆ octahedra. In these structures, two BO₄ tetrahedra and two PO₄ tetrahedra form helical chains, while the MgO₆ octahedra connect to four PO₄ tetrahedra through shared oxygen atoms, linking adjacent helical chains to form a three-dimensional (3D) framework. Alkaline metals (K, Na, Li) are situated within the voids of these frameworks. KMg[B(PO₄)₂](H₂O)₂, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O) exhibit moderate second harmonic generation (SHG) responses in the ultraviolet region, with of ∼0.13 × KDP, ∼0.10 × KDP and ∼0.17 × KDP, respectively. The syntheses and topological structures, elemental analyses, thermal stability, infrared spectroscopy, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy and NLO properties are discussed.

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混合碱性/碱土金属硼磷酸盐的合成、结构表征及非线性光学性质

硼磷酸盐由于其独特的结构特征和优异的性能而引起了人们的广泛关注。一价碱金属和二价碱土金属加入硼磷酸盐体系后，晶体结构明显多样化。采用低温水热法合成了一种新型硼磷酸盐KMg [B(PO4)2](H2O)2和两种非线性光学材料NaMg(H2O)2(BP2O8) （H2O）和LiMg(H2O)2(BP2O8) （H2O）。这些化合物在P6122的同一极性空间群中结晶。KMg [B(PO4)2](H2O)2、NaMg(H2O)2(BP2O8) （H2O）和LiMg(H2O)2(BP2O8) （H2O）的基本结构单元由BO4四面体、PO4四面体和MgO6八面体组成。在这些结构中，两个BO4四面体和两个PO4四面体形成螺旋链，而MgO6八面体通过共享氧原子与四个PO4四面体连接，连接相邻的螺旋链形成三维（3D）框架。碱金属（K, Na, Li）位于这些框架的空隙中。KMg[B(PO4)2](H2O)2、NaMg(H2O)2(BP2O8) （H2O）和LiMg(H2O)2(BP2O8) （H2O）在紫外区表现出中等的二次谐波产生（SHG）响应，分别为~ 0.13 × KDP、~ 0.10 × KDP和~ 0.17 × KDP。讨论了合成方法、拓扑结构、元素分析、热稳定性、红外光谱、拉曼光谱、UV-Vis漫反射光谱和NLO性能。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.