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[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response

[C(NH2)3]3PO4·2H2O: 一种具有大双折射和大倍频响应的新型无金属紫外磷酸盐非线性光学晶体

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Abstract

[PO4]3− possesses small microscopic second-order susceptibility and polarizability anisotropy, which inherently result in weak second-harmonic generation (SHG) and small birefringence. Herein, a new noncentrosymmetric phosphate, [C(NH2)3]3PO4·2H2O, was successfully designed and synthesized by a solution evaporation method. [C(NH2)3]3PO4·2H2O without metal ions is composed of planar conjugated guanidine cations and PO4 tetrahedrons, which are connected by hydrogen bonds, forming a three-dimensional network. Physical property measurements indicate that the title compound displays an SHG response of 1.5 × KH2PO4 (KDP) and a larger birefringence (0.055@546.1 nm) compared with most reported ultraviolet nonlinear optical phosphates. Furthermore, first-principles calculations reveal that the π-conjugated planar [C(NH2)3]+ cations and [PO4]3− groups are responsible for its excellent linear and NLO properties.

摘要

[PO4]3−具有较小的微观二阶极化率和极化各向异性, 这往往导致磷酸盐具有较小的倍频效应和双折射率. 本文采用溶液蒸发法设计并合成了新型非中心对称磷酸盐[C(NH2)3]3PO4·2H2O. 无金属离子的[C(NH2)3]3PO4·2H2O由平面共轭胍阳离子和磷酸根四面体组成, 并通过氢键连接形成三维网络. 物理性能测量表明, 与大多数报道的紫外非线性光学材料中的磷酸盐相比, 标题化合物显示出更大的双折射(0.055@546.1 nm)和大倍频响应(1.5 × KDP). 此外, 第一性原理计算表明, π共轭的平面[C(NH2)3]+阳离子和[PO4]3−基团是其优异的线性和非线性光学特性的来源.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21975255, 51890862, 21921001 and U1605245), the National Key Research and Development Plan of Ministry of Science and Technology (2016YFB0402104), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), the Natural Science Foundation of Fujian Province (2019J01020758), and Youth Innovation Promotion Association CAS (2019303).

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Authors and Affiliations

  1. College of Chemistry, Fuzhou University, Fuzhou, 350116, China

    Xin Wen  (温馨)

  2. Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Xin Wen  (温馨), Min Luo  (罗敏), Huixin Fan  (范慧欣), Kaichuang Chen  (陈开创) & Ning Ye  (叶宁)

  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Chensheng Lin  (林晨升)

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  1. Xin Wen  (温馨)
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  2. Chensheng Lin  (林晨升)
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  3. Min Luo  (罗敏)
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  4. Huixin Fan  (范慧欣)
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Contributions

Author contributions Wen X performed the experiments and data analysis, and wrote the paper; Lin C performed the theoretical calculation; Fan H measured the birefringence; Chen K offered help in analyzing experimental data; Luo M revised the manuscript. Ye N guided and supervised the experiments. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Min Luo  (罗敏) or Ning Ye  (叶宁).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Xin Wen received her BSc degree from Taiyuan University of Technology in 2018. She is currently a Master student jointly trained by Fuzhou University and Fujian Institute of Research on the Structure of Matter (FJIRSM) under the direction of Professor Ning Ye.

Min Luo received his BSc degree from Central South University in 2011 and PhD degree in material physics and chemistry from the University of Chinese Academy of Sciences in 2016. He has been an associate professor at FJIRSM since 2020. His current research interests include the design, synthesis, and crystal growth of new nonlinear optical materials.

Ning Ye received his BSc degree from Shanghai Jiao Tong University in 1993 and PhD degree in physical chemistry from FJIRSM in 1998 (Director: Academician Chuangtian Chen). From 1999 to 2004, he carried out postdoctoral research at the National University of Singapore, University of Texas at Austin and Oregon State University. He has been a full professor at FJIRSM since 2004. His current research interests include the design and growth of nonlinear optical crystals for deep-UV and mid-IR as well as growth of scintillation crystals.

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[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response

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Wen, X., Lin, C., Luo, M. et al. [C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response. Sci. China Mater. 64, 2008–2016 (2021). https://doi.org/10.1007/s40843-020-1604-0

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