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Syntheses, characterization, and theoretical calculation of Rb2Mg3(P2O7)2 polymorphs with deep-ultraviolet cutoff edges

拥有深紫外截止边的Rb2Mg3(P2O7)2同质多晶的合成、表征和理论计算

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Abstract

By the combination of the isolated P2O7 dimers and MgO4 tetrahedra, α- and β-Rb2Mg3(P2O7)2 polymorphs were synthesized by a high-temperature solution method. α-Rb2Mg3(P2O7)2 crystallizes in non-centrosymmetric space group P212121, while β-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 from α- to β-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.

摘要

本文结合孤立的P2O7二聚体和MgO4四面体, 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.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51972230, 51802217, 61835014, 51890864 and 51890865), the Natural Science Foundation of Tianjin (19JCZDJC38200), and the National Key Research and Development Project (2016YFB0402103).

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Authors and Affiliations

  1. Tianjin Key Laboratory of Functional Crystal Materials, Institute of Functional Crystal, Tianjin University of Technology, Tianjin, 300384, China

    Hongping Wu  (吴红萍), Shiwei Liu  (刘世伟), Hongwei Yu  (俞洪伟), Zhanggui Hu  (胡章贵), Jiyang Wang  (王继扬) & Yicheng Wu  (吴以成)

  2. Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi, 830011, China

    Shichao Cheng  (程世超)

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  1. Hongping Wu  (吴红萍)
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Contributions

Wu H, and Liu S performed the experiments, data analysis, and paper writing; Cheng S performed the theoretical data analysis; Yu H, Hu Z, Wang J and Wu Y designed the concept and supervised the experiments. All authors contributed to the general discussion.

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Correspondence to Hongwei Yu  (俞洪伟).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information The supporting data are available in the online version of the paper. Accession Codes: CCDC 1947460 and 1947461 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge viawww.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +441223 336033.

Hongping Wu received her PhD in 2012 from Xinjiang University. In the same year, she started her independent career as an associate professor at Xinjiang Technical Institute of Physics & Chemistry of CAS (XTIPC, CAS). In 2017, she was promoted to a full professor at XTIPC. From 2018, she has been working as a full professor at Tianjin University of Technology. Her current research interest focuses on new NLO materials.

Hongwei Yu received his PhD degree in material physics and chemistry from University of Chinese Academy of Sciences under the direction of Professor Shilie Pan. He did post-doctoral research at Houston University and Northwestern University in USA from 2014 to 2017. From 2018, he has been working as a full professor at Tianjin University of Technology. His current research interests include the design, synthesis, crystal growth, and evaluation of new optical electronic functional materials.

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Wu, H., Liu, S., Cheng, S. et al. Syntheses, characterization, and theoretical calculation of Rb2Mg3(P2O7)2 polymorphs with deep-ultraviolet cutoff edges. Sci. China Mater. 63, 593–601 (2020). https://doi.org/10.1007/s40843-019-1221-0

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