Citation: Yan-Qiang LI, Jun-Hua LUO, Xiang-Hai JI, San-Gen ZHAO. A Short-wave UV Nonlinear Optical Sulfate of High Thermal Stability[J]. Chinese Journal of Structural Chemistry, ;2020, 39(3): 485-492. doi: 10.14102/j.cnki.0254-5861.2011-2447 shu

A Short-wave UV Nonlinear Optical Sulfate of High Thermal Stability

Yan-Qiang LI ^{a, b, c, d} ,
Jun-Hua LUO ^{a, c, d} ,
Xiang-Hai JI ^e ,
San-Gen ZHAO ^a,,

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
c.
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
d.
University of the Chinese Academy of Sciences, Beijing 100049, China
e.
Shangdong Kangming Environmental Protection Co. Ltd., Dongying, Shangdong 257000, China

Corresponding author: San-Gen ZHAO, zhaosangen@fjirsm.ac.cn
Received Date: 6 May 2019
Accepted Date: 24 July 2019

Fund Project: the National Natural Science Foundation of China 21833010the National Natural Science Foundation of China 21571178the National Natural Science Foundation of China 21601188the National Natural Science Foundation of China 51872297the National Natural Science Foundation of China 51802321

Figures(5)

Compared with borates, carbonates, nitrates and phosphates, sulfates have been ignored as nonlinear optical (NLO) materials for a long time. Recently, researchers started to realize sulfates which have the potential as NLO materials, and synthesized some sulfate NLO materials by the water solution method and solvothermal method. However, all these sulfate NLO materials have the same problem of low thermal stability. Here, we synthesized a new Cs₄Mg₆(SO₄)₈, which crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 9.102, b = 9.955, c = 16.127 Å, V = 1461.3 Å³, Z = 2, F(000) = 1352, μ = 5.777 mm^-1, R = 0.0213 and wR = 0.0480. The single crystal structure can be described as a three-dimensional framework constructed by MgO₆ octahedra and SO₄ tetrahedra. Relevant optical measurements indicate that Cs₄Mg₆(SO₄)₈ is short-wave ultraviolet transparent and has a moderate second harmonic generation response. Theoretical calculations by the CASTEP package reveal that S–O groups are NLO-active anionic groups. Significantly, Cs₄Mg₆(SO₄)₈ has high thermal stability up to 781 ℃ based on thermal analyses. We believe that our work will provide a new strategy for researchers to develop new sulfate short-wave ultraviolet NLO materials of high thermal stability.
- sulfates,
- nonlinear optical materials,
- thermal stability,
- short-wave ultraviolet,
- flux method
1. [1]
  Cyranoski, D. Materials science: China's crystal cache. Nature 2009, 457, 953–955. doi: 10.1038/457953a
2. [2]
  Chen, C.; Wu, Y.; Jiang, A.; Wu, B.; You, G.; Li, R.; Lin, S. New nonlinear optical crystal: LiB₃O₅. J. Opt. Soc. Am. B 1989, 6, 616–621. doi: 10.1364/JOSAB.6.000616
3. [3]
  Chen, C.; Wu, B.; Jiang, A.; You, G. A new-type ultraviolet SHG crystal β-BaB₂O₄. Sci. Sin. B 1985, 28, 235–241.
4. [4]
  De Yoreo, J. J.; Burnham, A. K.; Whitman, P. K. Developing KH₂PO₄ and KD₂PO₄ crystals for the world's most power laser. Int. Mater. Rev. 2002, 47, 113–152. doi: 10.1179/095066001225001085
5. [5]
  Chen, C. T.; Wang, G. L.; Wang, X. Y.; Xu, Z. Y. Deep-UV nonlinear optical crystal KBe₂BO₃F₂-discovery, growth, optical properties and applications. Appl. Phys. B 2009, 97, 9–25. doi: 10.1007/s00340-009-3554-4
6. [6]
  Chen, C.; Wang, Y.; Wu, B.; Wu, K.; Zeng, W.; Yu, L. Design and synthesis of an ultraviolet-transparent nonlinear optical crystal Sr₂Be₂B₂O₇. Nature 1995, 373, 322–324. doi: 10.1038/373322a0
7. [7]
  Huang, H. W.; Liu, L. J.; Jin, S. F.; Yao, W. J.; Zhang, Y. H.; Chen, C. T. Deep-ultraviolet nonlinear optical materials: Na₂Be₄B₄O₁₁ and LiNa₅Be₁₂B₁₂O₃₃. J. Am. Chem. Soc. 2013, 135, 18319–18322. doi: 10.1021/ja410543w
8. [8]
  Zhao, S.; Gong, P.; Bai, L.; Xu, X.; Zhang, S.; Sun, Z.; Lin, Z.; Hong, M.; Chen, C.; Luo, J. Beryllium-free Li₄Sr(BO₃)₂ for deep-ultraviolet nonlinear optical applications. Nat. Commun. 2014, 5, 4019–4025. doi: 10.1038/ncomms5019
9. [9]
  Tran, T. T.; Koocher, N. Z.; Rondinelli, J. M.; Halasyamani, P. S. Beryllium-free beta-Rb₂Al₂B₂O₇ as a possible deep-ultraviolet nonlinear optical material replacement for KBe₂BO₃F₂. Angew. Chem. Int. Ed. 2017, 56, 2969–2973. doi: 10.1002/anie.201612236
10. [10]
  Shi, G.; Wang, Y.; Zhang, F.; Zhang, B.; Yang, Z.; Hou, X.; Pan, S.; Poeppelmeier, K. R. Finding the next deep-ultraviolet nonlinear optical material: NH₄B₄O₆F. J. Am. Chem. Soc. 2017, 139, 10645–10648. doi: 10.1021/jacs.7b05943
11. [11]
  Wang, X. F.; Wang, Y.; Zhang, B. B.; Zhang, F. F.; Yang, Z. H.; Pan, S. L. CsB₄O₆F: a congruent-melting deep-ultraviolet nonlinear optical material by combining superior functional units. Angew. Chem. Int. Ed. 2017, 56, 14119–14123. doi: 10.1002/anie.201708231
12. [12]
  Luo, M.; Fei, L.; Song, Y. X.; Zhao, D.; Xu, F.; Ye, N.; Lin, Z. S. M₂B₁₀O₁₄F₆ (M = Ca, Sr): two noncentrosymmetric alkaline earth fluorooxoborates as promising next-heneration deep-ultraviolet nonlinear optical materials. J. Am. Chem. Soc. 2018, 140, 6509–6509. doi: 10.1021/jacs.8b04744
13. [13]
  Zhang, Z. Z.; Wang, Y.; Zhang, B. B.; Yang, Z. H.; Pan, S. L. CaB₅O₇F₃: a beryllium-free alkaline-earth fluorooxoborate exhibiting excellent nonlinear optical performances. Inorg. Chem. 2018, 57, 4820–4823. doi: 10.1021/acs.inorgchem.8b00531
14. [14]
  Zou, G.; Ye, N.; Huang, L.; Lin, X. Alkaline-alkaline earth fluoride carbonate crystals ABCO₃F (A = K, Rb, Cs; B = Ca, Sr, Ba) as nonlinear optical materials. J. Am. Chem. Soc. 2011, 133, 20001–20007. doi: 10.1021/ja209276a
15. [15]
  Tran, T. T.; He, J. G.; Rondinelli, J. M.; Halasyamani, P. S. RbMgCO₃F: a new beryllium-free deep-ultraviolet nonlinear optical material. J. Am. Chem. Soc. 2015, 137, 10504–10507. doi: 10.1021/jacs.5b06519
16. [16]
  Peng, G.; Lin, C. S.; Yang, Y.; Zhao, D.; Lin, Z.; Ye, N.; Huang, J. S. Y₂(CO₃)₃·H₂O and (NH₄)₂Ca₂Y₄(CO₃)₉·H₂O: partial aliovalent cation substitution enabling evolution from centrosymmetry to noncentrosymmetry for nonlinear optical response. Chem. Mater. 2019, 31, 52–56. doi: 10.1021/acs.chemmater.8b04428
17. [17]
  Zou, G. H.; Lin, C. S.; Kim, H. G.; Jo, H.; Ok, K. M. Rb₂Na(NO₃)₃: a congruently melting UV-NLO crystal with a very strong second-harmonic generation response. Crystals 2016, 6, 42–55. doi: 10.3390/cryst6040042
18. [18]
  Song, Y.; Luo, M.; Lin, C.; Ye, N. Structural modulation of nitrate group with cations to affect SHG responses in RE(OH)₂NO₃ (RE = La, Y, and Gd): new polar materials with large NLO effect after adjusting pH values of reaction systems. Chem. Mater. 2017, 29, 896–903. doi: 10.1021/acs.chemmater.6b05119
19. [19]
  Chen, J.; Xiong, L.; Chen, L.; Wu, L. M. Ba₂NaCIP₂O₇: unprecedented phase matchability induced by symmetry breaking and its unique fresnoite-type structure. J. Am. Chem. Soc. 2018, 140, 14082–14086. doi: 10.1021/jacs.8b10209
20. [20]
  Yu, H.; Young, J.; Wu, H.; Zhang, W.; Rondinelli, J. M.; Halasyamani, P. S. M₄Mg₄(P₂O₇)₃ (M = K, Rb): structural engineering of pyrophosphates for nonlinear optical applications. Chem. Mater. 2017, 29, 1845–1855. doi: 10.1021/acs.chemmater.7b00167
21. [21]
  Shen, Y. G.; Yang, Y.; Zhao, S. G.; Zhao, B. Q.; Lin, Z. S.; Ji, C. M.; Li, L. N.; Fu, P.; Hong, M. C.; Luo, J. H. Deep-ultraviolet transparent Cs₂LiPO₄ exhibits an unprecedented second harmonic generation. Chem. Mater. 2016, 28, 7110–7116. doi: 10.1021/acs.chemmater.6b03333
22. [22]
  Li, L.; Wang, Y.; Lei, B. H.; Han, S. J.; Yang, Z. H.; Poeppelmeier, K. R.; Pan, S. L. A new deep-ultraviolet transparent orthophosphate LiCs₂PO₄ with large second harmonic generation response. J. Am. Chem. Soc. 2016, 138, 9101–9104. doi: 10.1021/jacs.6b06053
23. [23]
  Zhao, S. G.; Gong, P. F.; Luo, S. Y.; Bai, L.; Lin, Z. S.; Tang, Y. Y.; Zhou, Y. L.; Hong, M. C.; Luo, J. H. Tailored synthesis of a nonlinear optical phosphate with a short absorption edge. Angew. Chem. Int. Ed. 2015, 54, 4217–4221. doi: 10.1002/anie.201411772
24. [24]
  Zhao, S. G.; Gong, P. F.; Luo, S. Y.; Bai, L.; Lin, Z. S.; Ji, C. M.; Chen, T. L.; Hong, M. C.; Luo, J. H. Deep-ultraviolet transparent phosphates RbBa₂(PO₃)₅ and Rb₂Ba₃(P₂O₇)₂ show nonlinear optical activity from condensation of [PO₄]^3- units. J. Am. Chem. Soc. 2014, 36, 8560–8563.
25. [25]
  Yu, P.; Wu, L. M.; Zhou, L. J.; Chen, L. Deep-ultraviolet nonlinear optical crystals: Ba₃P₃O₁₀X (X = Cl, Br). J. Am. Chem. Soc. 2014, 36, 480–487.
26. [26]
  He, F.; Wang, Q.; Hu, C.; He, W.; Luo, X.; Huang, L.; Gao, D.; Bi, J.; Wang, X.; Zou, G. Centrosymmetric (NH₄)₂SbCl(SO₄)₂ and non-centrosymmetric (NH₄)SbCl₂(SO₄): synergistic effect of hydrogen-bonding interactions and lone-pair cations on the framework structures and macroscopic centricities. Cryst. Growth Des. 2018, 8, 6239–6247.
27. [27]
  Li, Y.; Zhao, S.; Shan, P.; Li, X.; Ding, Q.; Liu, S.; Wu, Z.; Wang, S.; Li, L.; Luo, J. Li₈NaRb₃(SO₄)₆·2H₂O as a new sulfate deep-ultraviolet nonlinear optical material. J. Mater. Chem. C 2018, 6, 12240–12244. doi: 10.1039/C8TC04361B
28. [28]
  Li, Y.; Liang, F.; Zhao, S.; Li, L.; Wu, Z.; Ding, Q.; Liu, S.; Lin, Z.; Hong, M.; Luo, J. Two non-π-conjugated deep-UV nonlinear optical sulfates. J. Am. Chem. Soc. 2019, 141, 3833–3837. doi: 10.1021/jacs.9b00138
29. [29]
  Dong, X.; Huang, L.; Hu, C.; Zeng, H.; Lin, Z.; Wang, X.; Ok, K. M.; Zou, G. CsSbF₂SO₄: an excellent ultraviolet nonlinear optical sulfate with a KTiOPO₄ (KTP)-type structure. Angew. Chem. Int. Ed. 2019, accepted.
30. [30]
  SAINT A. APEX3 software for CCD Diffractometers. Bruker Analytical X-ray Systems Inc. Madison, WI 2014.
31. [31]
  Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. Sect. A: Found. Crystallogr. 2008, 64, 112–122. doi: 10.1107/S0108767307043930
32. [32]
  Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7–13. doi: 10.1107/S0021889802022112
33. [33]
  Tauc, J. Absorption edge and internal electric fields in amorphous semiconductors. Mater. Res. Bull. 1970, 5, 721–729. doi: 10.1016/0025-5408(70)90112-1
34. [34]
  Clark, S. J.; Segall, M. D.; Pickard, C. J.; Hasnip, P. J.; Probert, M. J.; Refson, K.; Payne, M. C. First principles methods using CASTEP. Z. Kristallogr. 2005, 220, 567–570.
35. [35]
  Rappe, A. M.; Rabe, K. M.; Kaxiras, E.; Joannopoulos, J. D. Optimized pseudopotentials. Phys. Rev. B 1990, 41, 1227–1230. doi: 10.1103/PhysRevB.41.1227
1. [1]
  Rongliang Deng , Yihang Chen , Xiaotong Fan , Guolong Chen , Shuli Wang , Changzhi Yu , Xiao Yang , Tingzhu Wu , Zhong Chen , Yue Lin . Break of thermal equilibrium between optical and acoustic phonon branches of CsPbI₃ under continuous-wave light excitation and cryogenic temperature. Chinese Chemical Letters, 2024, 35(7): 109346-. doi: 10.1016/j.cclet.2023.109346
2. [2]
  Jiajing Wu , Ru-Ling Tang , Sheng-Ping Guo . Three types of promising functional building units for designing metal halide nonlinear optical crystals. Chinese Journal of Structural Chemistry, 2024, 43(6): 100291-100291. doi: 10.1016/j.cjsc.2024.100291
3. [3]
  Ningning Gao , Yue Zhang , Zhenhao Yang , Lijing Xu , Kongyin Zhao , Qingping Xin , Junkui Gao , Junjun Shi , Jin Zhong , Huiguo Wang . Ba²⁺/Ca²⁺ co-crosslinked alginate hydrogel filtration membrane with high strength, high flux and stability for dye/salt separation. Chinese Chemical Letters, 2024, 35(5): 108820-. doi: 10.1016/j.cclet.2023.108820
4. [4]
  Xiping Dong , Xuan Wang , Zhixiu Lu , Qinhao Shi , Zhengyi Yang , Xuan Yu , Wuliang Feng , Xingli Zou , Yang Liu , Yufeng Zhao . Construction of Cu-Zn Co-doped layered materials for sodium-ion batteries with high cycle stability. Chinese Chemical Letters, 2024, 35(5): 108605-. doi: 10.1016/j.cclet.2023.108605
5. [5]
  Pu Zhang , Xiang Mao , Xuehua Dong , Ling Huang , Liling Cao , Daojiang Gao , Guohong Zou . Two UV organic-inorganic hybrid antimony-based materials with superior optical performance derived from cation-anion synergetic interactions. Chinese Chemical Letters, 2024, 35(9): 109235-. doi: 10.1016/j.cclet.2023.109235
6. [6]
  Zhiwei Zhong , Yanbin Huang , Wantai Yang . A simple photochemical method for surface fluorination using perfluoroketones. Chinese Chemical Letters, 2024, 35(5): 109339-. doi: 10.1016/j.cclet.2023.109339
7. [7]
  Juan Guo , Mingyuan Fang , Qingsong Liu , Xiao Ren , Yongqiang Qiao , Mingju Chao , Erjun Liang , Qilong Gao . Zero thermal expansion in Cs₂W₃O₁₀. Chinese Chemical Letters, 2024, 35(7): 108957-. doi: 10.1016/j.cclet.2023.108957
8. [8]
  Erzhuo Cheng , Yunyi Li , Wei Yuan , Wei Gong , Yanjun Cai , Yuan Gu , Yong Jiang , Yu Chen , Jingxi Zhang , Guangquan Mo , Bin Yang . Galvanostatic method assembled ZIFs nanostructure as novel nanozyme for the glucose oxidation and biosensing. Chinese Chemical Letters, 2024, 35(9): 109386-. doi: 10.1016/j.cclet.2023.109386
9. [9]
  Keyang Li , Yanan Wang , Yatao Xu , Guohua Shi , Sixian Wei , Xue Zhang , Baomei Zhang , Qiang Jia , Huanhua Xu , Liangmin Yu , Jun Wu , Zhiyu He . Flash nanocomplexation (FNC): A new microvolume mixing method for nanomedicine formulation. Chinese Chemical Letters, 2024, 35(10): 109511-. doi: 10.1016/j.cclet.2024.109511
10. [10]
  Xinzhi Ding , Chong Liu , Jing Niu , Nan Chen , Shutao Xu , Yingxu Wei , Zhongmin Liu . Solid-state NMR study of the stability of MOR framework aluminum. Chinese Journal of Structural Chemistry, 2024, 43(4): 100247-100247. doi: 10.1016/j.cjsc.2024.100247
11. [11]
  Jingyuan Yang , Xinyu Tian , Liuzhong Yuan , Yu Liu , Yue Wang , Chuandong Dou . Enhancing stability of diradical polycyclic hydrocarbons via P=O-attaching. Chinese Chemical Letters, 2024, 35(8): 109745-. doi: 10.1016/j.cclet.2024.109745
12. [12]
  Ting Wang , Xin Yu , Yaqiang Xie . Unlocking stability: Preserving activity of biomimetic catalysts with covalent organic framework cladding. Chinese Chemical Letters, 2024, 35(6): 109320-. doi: 10.1016/j.cclet.2023.109320
13. [13]
  Tao LIU , Yuting TIAN , Ke GAO , Xuwei HAN , Ru'nan MIN , Wenjing ZHAO , Xueyi SUN , Caixia YIN . A photothermal agent with high photothermal conversion efficiency and high stability for tumor therapy. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1622-1632. doi: 10.11862/CJIC.20240107
14. [14]
  Ruizhi Yang , Xia Li , Weiping Guo , Zixuan Chen , Hongwei Ming , Zhong-Zhen Luo , Zhigang Zou . New thermoelectric semiconductors Pb5Sb12+xBi6-xSe32 with ultralow thermal conductivity. Chinese Journal of Structural Chemistry, 2024, 43(3): 100268-100268. doi: 10.1016/j.cjsc.2024.100268
15. [15]
  Chaozheng He , Pei Shi , Donglin Pang , Zhanying Zhang , Long Lin , Yingchun Ding . First-principles study of the relationship between the formation of single atom catalysts and lattice thermal conductivity. Chinese Chemical Letters, 2024, 35(6): 109116-. doi: 10.1016/j.cclet.2023.109116
16. [16]
  Ying Li , Long-Jie Wang , Yong-Kang Zhou , Jun Liang , Bin Xiao , Ji-Shen Zheng . An improved installation of 2-hydroxy-4-methoxybenzyl (iHmb) method for chemical protein synthesis. Chinese Chemical Letters, 2024, 35(5): 109033-. doi: 10.1016/j.cclet.2023.109033
17. [17]
  Peng Zhou , Ziang Jiang , Yang Li , Peng Xiao , Feixiang Wu . Sulphur-template method for facile manufacturing porous silicon electrodes with enhanced electrochemical performance. Chinese Chemical Letters, 2024, 35(8): 109467-. doi: 10.1016/j.cclet.2023.109467
18. [18]
  Haoyang Wang , Ronghao Zhang , Yanlun Ren , Li Zhang . A convenient method for measuring gas-liquid volumetric mass transfer coefficient in micro reactors. Chinese Chemical Letters, 2024, 35(4): 108833-. doi: 10.1016/j.cclet.2023.108833
19. [19]
  Ting Li , Xinxin Zheng , Lejing Qu , Yuanyuan Ou , Sai Qiao , Xue Zhao , Yajun Zhang , Xinfeng Zhao , Qian Li . A chromatographic method for pursuing potential GPCR ligands with the capacity to characterize their intrinsic activities of regulating downstream signaling pathway. Chinese Chemical Letters, 2024, 35(10): 109792-. doi: 10.1016/j.cclet.2024.109792
20. [20]
  Yi Herng Chan , Zhe Phak Chan , Serene Sow Mun Lock , Chung Loong Yiin , Shin Ying Foong , Mee Kee Wong , Muhammad Anwar Ishak , Ven Chian Quek , Shengbo Ge , Su Shiung Lam . Thermal pyrolysis conversion of methane to hydrogen (H₂): A review on process parameters, reaction kinetics and techno-economic analysis. Chinese Chemical Letters, 2024, 35(8): 109329-. doi: 10.1016/j.cclet.2023.109329

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(456)
HTML views(17)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142