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From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement

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Abstract

The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination, electronegativity, and according anionic framework. Here, we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution. A new borophosphate Ba2BP3O11 with the monoclinic space group P21/c has been synthesized in the sealed system. Ba2BP3O11 exhibits a rare P–O–P bridge formation, which is the first example in alkaline-earth metal borophosphates. By further substituting [BO4]3− with [BO3F]4−, the first alkaline-earth metal/lead fluoroborophosphates M2BP2O8F (M = Ba and Pb) with the same space group were designed. Since the scissors effect of fluorine, in M2BP2O8F (M = Ba and Pb), a BO3F tetrahedron corner-sharing with three PO4 tetrahedra forms 1D chains along the b-axial direction, which are filled by MOn (M = Ba/Pb, n = 5, 6, 8) distorted polyhedra. The first principles calculation shows that the borophosphate Ba2BP3O11 has a birefringence about 0.013 @1,064 nm, while the fluoroborophosphates M2BP2O8F (M = Ba and Pb) have the values of 0.035 and 0.043 @1,064 nm, respectively. Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation. The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51972336, 61835014, 51922014), the International Partnership Program of CAS (1A1365KYSB20200008), the Instrument Developing Project of CAS (GJJSTD20200007), the Science and Technology Service Network Initiative of CAS (KFJ-STS-QYZD-130), Basic Frontier Science Research Program of CAS (ZDBS-LY-SLH035), and the Western Light Foundation of CAS (Y92S191301), Fujian Institute of Innovation, CAS (FJCXY18010202).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. CAS Key Laboratory of Functional Materials and Devices for Special Environments; Xinjiang Technical Institute of Physics & Chemistry, CAS; Xinjiang Key Laboratory of Electronic Information Materials and Devices, Urumqi, 830011, China

    Wenyao Zhang, Zhizhong Zhang, Wenqi Jin, Ruonan Zhang, Meng Cheng, Zhihua Yang & Shilie Pan

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Wenyao Zhang, Zhizhong Zhang, Wenqi Jin, Ruonan Zhang, Meng Cheng, Zhihua Yang & Shilie Pan

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  1. Wenyao Zhang
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  2. Zhizhong Zhang
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  3. Wenqi Jin
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  4. Ruonan Zhang
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  6. Zhihua Yang
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  7. Shilie Pan
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Correspondence to Zhihua Yang or Shilie Pan.

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Zhang, W., Zhang, Z., Jin, W. et al. From borophosphate to fluoroborophosphate: a rational design of fluorine-induced birefringence enhancement. Sci. China Chem. 64, 1498–1503 (2021). https://doi.org/10.1007/s11426-021-1024-5

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  • DOI: https://doi.org/10.1007/s11426-021-1024-5

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