摘要
本文结合孤立的P2O7二聚体和Mg O4四面体,采用高温熔液法合成了α和β-Rb2Mg3(P2O7)2同质多晶.α-Rb2Mg3(P2O7)2结晶于非中心对称P212121空间群,β-Rb2Mg3(P2O7)2结晶于中心对称P21/c空间群.两种结构均含有三维[Mg3P4O14]^2-阴离子骨架,而Rb+离子位于空间中.结构分析表明,孤立的P2O7通过调整其可变构型和取向以适合不同配位环境的阳离子,这有利于同质多晶Rb2Mg3(P2O7)2的形成.另外,从α-到β-Rb2Mg3(P2O7)2的相转变过程也可以通过粉末X射线衍射和热重-差热测试被进一步证明.紫外-可见-近红外漫反射光谱测试表明两种材料都有深紫外截止边(190 nm以下),并且α-Rb2Mg3(P2O7)2具有倍频效应,我们通过倍频密度计算研究了其倍频效应的来源.为了更好地理解上述化合物的结构性能关系,我们还进行了第一性原理计算.
By the combination of the isolated P2O7 dimers and Mg O4 tetrahedra,α-andβ-Rb2Mg3(P2O7)2 polymorphs were synthesized by a high-temperature solution method.α-Rb2Mg3(P2O7)2 crystallizes in non-centrosymmetric space group P212121,whileβ-Rb2Mg3(P2O7)2 crystallizes in centrosymmetric P21/c.Both structures contain a three dimensional[Mg3P4O14]^2- anionic framework,while Rb^+ cations are in the space.Structure analyses show that the isolated P2O7 dimers can easily adjust their variable configurations and orientations to fit the different coordination environments of the cations,which is conducive to the formation of polymorphs.The phase transformation process fromα-toβ-Rb2Mg3(P2O7)2 was further investigated by powder X-ray diffraction and thermal gravimetric/differential scanning calorimetry measurements.In addition,UV-vis-NIR diffusion spectra indicate both materials have deep-ultraviolet cut-off edges(below 190 nm).α-Rb2Mg3(P2O7)2 is second-harmonic generation(SHG)-active and the origin of SHG response was investigated by the SHG density calculations.The first-principle calculations were also carried out to illuminate their structure-property relationships.
作者
吴红萍
刘世伟
程世超
俞洪伟
胡章贵
王继扬
吴以成
Hongping Wu;Shiwei Liu;Shichao Cheng;Hongwei Yu;Zhanggui Hu;Jiyang Wang;Yicheng Wu(Tianjin Key Laboratory of Functional Crystal Materials,Institute of Functional Crystal,Tianjin University of Technology,Tianjin 300384,China;Xinjiang Technical Institute of Physics&Chemistry,Chinese Academy of Sciences,Urumqi 830011,China)
基金
financially supported by the National Natural Science Foundation of China (51972230, 51802217, 61835014, 51890864 and 51890865)
the Natural Science Foundation of Tianjin (19JCZDJC38200)
the National Key Research and Development Project (2016YFB0402103)