Citation: Wenbo LIU, Chunbo JIANG, Chao WU, Zhipeng HUANG, Chi ZHANG. A UV transparent rare earth metal formate exhibiting second harmonic generation response and moderate birefringence[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(1): 281-288. doi: 10.11862/CJIC.20230429 shu

A UV transparent rare earth metal formate exhibiting second harmonic generation response and moderate birefringence

China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China

Corresponding author: Chao WU, wuc@tongji.edu.cn Chi ZHANG, chizhang@tongji.edu.cn
Received Date: 13 November 2023
Revised Date: 6 December 2023

Figures(6)

A rare earth metal formate, (C(NH₂)₃)[Er(HCOO)₄], was prepared via an evaporation method. Benefiting from its non-centrosymmetric structure, optical property studies reveal that (C(NH₂)₃)[Er(HCOO)₄] possessed a wide optical bandgap of 4.76 eV, moderate birefringence (0.066@546 nm), second harmonic generation (SHG) response (0.20 times that of KH₂PO₄ (KDP)), and phase-matchable capabilities at 1 064 nm. Theoretical calculations and crystal structure analysis revealed that the optical properties can be attributed to the synergy effects of the (C(NH₂)₃)⁺, [ErO₈], and HCOO^- units.
- formates,
- second harmonic generation,
- birefringence,
- first-principles calculation
1. [1]
  Zeng W, Tian Y, Huang L, Zeng H, Lin Z E, Zou G H. [C(NH₂)₃]₂ MoO₂F₄·H₂O: Unique Chinese-knot structure revealing superior nonlinear-optical properties[J]. Inorg. Chem., 2022,61(37):14523-14527. doi: 10.1021/acs.inorgchem.2c02861
2. [2]
  Dong W M, Sun Y J, Wang B, Zhu M Q, Li J, Xu X G, Wang J Y. Bi₃TeBO₉: A promising mid-infrared nonlinear optical crystal with a large laser damage threshold[J]. Inorg. Chem., 2022,61(23):8870-8878. doi: 10.1021/acs.inorgchem.2c00924
3. [3]
  Wu C, Lin L, Jiang X X, Lin Z S, Huang Z P, Humphrey M G, Halasyamani P S, Zhang C. K₅(W₃O₉F₄)(IO₃): An efficient mid-infrared nonlinear optical compound with high laser damage threshold[J]. Chem. Mater., 2019,31(24):10100-10108. doi: 10.1021/acs.chemmater.9b03214
4. [4]
  Chen C T, Wu B C, Jiang A D, You G M. A new-type ultraviolet SHG crystal-β-BaB₂O₄[J]. Scientia Sinica Series B-Chemical Biological Agricultural Medical & Earth Sciences, 1985,28(3):235-243.
5. [5]
  Chen C T, Wu Y C, Jiang A, Wu B, You G, Li R, Lin S. New nonlinear-optical crystal: LiB₃O₅[J]. J. Opt. Soc. Am., 1989,6(4):616-621. doi: 10.1364/JOSAB.6.000616
6. [6]
  Tu J M, Keszler D A. CsLiB₆O₁₀-A noncentrosymmetric polyborate[J]. Mater. Res. Bull., 1995,30(2):209-215. doi: 10.1016/0025-5408(94)00121-9
7. [7]
  Liu Y S, Jones W B, Chernoch J P. High-efficiency high-power coherent UV generation at 266 nm in 90° phase-matched deuterated KDP[J]. Appl. Phys. Lett., 1976,29(1):32-34. doi: 10.1063/1.88861
8. [8]
  Tell B, Kasper H M. Optical and electrical properties of AgGaS₂ and AgGaSe₂[J]. Phys. Rev. B, 1971,4(12):4455-4459. doi: 10.1103/PhysRevB.4.4455
9. [9]
  Budni P A, Pomeranz L A, Lemons M L, Miller C A, Mosto J R, Chicklis E P. Efficient mid-infrared laser using 1.9-µm-pumped Ho: YAG and ZnGeP₂ optical parametric oscillators[J]. J. Opt. Soc. Am., 2000,17(5):723-728. doi: 10.1364/JOSAB.17.000723
10. [10]
  Luo M, Lin C, Lin D, Ye N. Rational design of the metal-free KBe₂BO₃F₂ (KBBF) family member C(NH₂)₃SO₃F with ultraviolet optical nonlinearity[J]. Angew. Chem. Int. Ed., 2020,59(37):15978-15981. doi: 10.1002/anie.202006671
11. [11]
  Kim E A, Lee D W, Ok K M. Centrosymmetric [N(CH₃)₄]₂TiF₆ vs. noncentrosymmetric polar [C(NH₂)₃]₂TiF₆: A hydrogen-bonding effect on the out-of-center distortion of TiF₆ octahedra[J]. J. Solid State Chem., 2012,195:149-154. doi: 10.1016/j.jssc.2011.11.027
12. [12]
  Hou W, Xu D F, Yuan D R, Liu M, Zhang N, Tao X, Sun S, Jiang M H. Investigations on triallylthiourea mercury bromide (ATMB) crystal growth[J]. Cryst. Res. Technol., 1994,29:939-944. doi: 10.1002/crat.2170290705
13. [13]
  Chen C T, Wu Y C, Li R. The anionic group theory of the non-linear optical effect and its applications in the development of new high-quality NLO crystals in the borate series[J]. Int. Rev. Phys. Chem., 2008,8(1):65-91.
14. [14]
  Shen Y, Zhao S G, Luo J H. The role of cations in second-order nonlinear optical materials based on π-conjugated [BO₃]^3- groups[J]. Coord. Chem. Rev., 2018,366:1-28. doi: 10.1016/j.ccr.2018.03.012
15. [15]
  Liu X, Gong P, Yang Y, Song G, Lin Z. Nitrate nonlinear optical crystals: A survey on structure-performance relationships[J]. Coord. Chem. Rev., 2019,400213045. doi: 10.1016/j.ccr.2019.213045
16. [16]
  Liu Y, Shen Y, Zhao S G, Luo J H. Structure-property relationship in nonlinear optical materials with π-conjugated CO₃ triangles[J]. Coord. Chem. Rev., 2020,407213152. doi: 10.1016/j.ccr.2019.213152
17. [17]
  Gong P F, Liu X, Kang L, Lin Z S. Inorganic planar π-conjugated groups in nonlinear optical crystals: Review and outlook[J]. Inorg. Chem. Front., 2020,7(4):839-852. doi: 10.1039/C9QI01589B
18. [18]
  Zhao T M, Chen S, Shang R, Wang B W, Wang Z M, Gao S. Perovskite-like polar lanthanide formate frameworks of [NH₂NH₃] [Ln(HCOO)₄] (Ln=Tb-Lu and Y): Synthesis, structures, magnetism, and anisotropic thermal expansion[J]. Inorg. Chem., 2016,55(20):10075-10082. doi: 10.1021/acs.inorgchem.6b00952
19. [19]
  Zhou Z Q, Shui Q R, Fu R B, Fang Y B, Ma Z J, Wu X T. KCs₂[Pb₂Br₅(HCOO)₂]: A polar 3D lead-bromide framework exhibiting strong second-harmonic generation response[J]. Chem.-Eur. J., 2021,27(51):12976-12980. doi: 10.1002/chem.202102332
20. [20]
  Yuan F F, Sun S J, Huang Y S, Zhang L Z, Lin Z B, Wang G F. Improvement of second-harmonic generation induced by structural distortions in Nb doped YCa₉(VO₄)₇ crystals[J]. J. Alloy. Compd., 2017,726:860-865. doi: 10.1016/j.jallcom.2017.08.064
21. [21]
  Zou G H, Jo H, Lim S J, You T S, Ok K M. Rb₃VO(O₂)₂CO₃: A four-in-one carbonatoperoxovanadate exhibiting an extremely strong second-harmonic generation response[J]. Angew. Chem. Int. Ed., 2018,57(28):8619-8622. doi: 10.1002/anie.201804354
22. [22]
  Kong F, Hu C L, Xu X, Zhou T H, Mao J G. Syntheses, crystal structures and SHG properties of a series of polar alkali-metal molybdenum? selenites based on Strandberg-type [Mo₅O₁₅(SeO₃)₂]^4- polyanion[J]. Dalton Trans., 2012,41(18):5687-5695. doi: 10.1039/c2dt12437h
23. [23]
  Cheng H, Jin W, Yang Z, Pan S. Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects[J]. Inorg. Chem. Front., 2022,9(17):4554-4568. doi: 10.1039/D2QI00990K
24. [24]
  Liu Y, Liu X, Xiong Z, Liu B, Xu J, Li L, Zhao S, Lin Z, Hong M, Luo J. 2D van der Waals layered [C(NH₂)₃]₂SO₃S exhibits desirable UV nonlinear-optical trade-off[J]. Inorg. Chem., 2021,60(19):14544-14549. doi: 10.1021/acs.inorgchem.1c02555
25. [25]
  Wen X, Lin C S, Luo M, Fan H, Chen K C, Ye N. [C(NH₂)₃]₃PO₄·2H₂O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response[J]. Sci. China Mater., 2021,64(8):2008-2016. doi: 10.1007/s40843-020-1604-0
26. [26]
  Yan D, Ren M M, Liu Q, Mao F F, Ma Y, Tang R L, Huang H, Zhang B, Zhang X D, Li S F. [C(NH₂)₂NHNO₂][C(NH₂)₃](NO₃)₂: A mixed organic cationic hybrid nitrate with an unprecedented nonlinear-optical-active unit[J]. Inorg. Chem., 2023,62(12):4757-4761. doi: 10.1021/acs.inorgchem.3c00556
27. [27]
  Zhang M, Zhang B B, Yang D, Wang Y. Synergistic effect of π-conjugated [C(NH₂)₃] cation and Sb? lone pair stereoactivity on structural transformation and second harmonic generation[J]. Inorg. Chem., 2021,60(23):18483-18489. doi: 10.1021/acs.inorgchem.1c03050
28. [28]
  Luo M, Lin C, Lin D, Ye N. Rational design of the metal-free KBe₂BO₃F₂⋅(KBBF) family member C(NH₂)₃SO₃F with ultraviolet optical nonlinearity[J]. Angew. Chem. Int. Ed., 2020,59(37):15978-15981. doi: 10.1002/anie.202006671
29. [29]
  Wu C, Jiang X X, Wang Z J, Sha H Y, Lin Z S, Huang Z P, Long X F, Mark G H, Zhang C. UV solar-blind-region phase-matchable optical nonlinearity and anisotropy in a π-conjugated cation-containing phosphate[J]. Angew. Chem. Int. Ed., 2021,60(27):14806-14810. doi: 10.1002/anie.202102992
30. [30]
  Liu B, Zheng H B, Wang Z M, Gao S. Chiral crystalline solids of ammonium-templated Er^Ⅲ-formate frameworks assembled from three achiral acentric components[J]. CrystEngComm, 2011,13:5285-5288. doi: 10.1039/c1ce05250k
31. [31]
  Wendlandt W M, Hecht H G. Reflectance spectroscopy. New York: Interscience, 1966.
32. [32]
  Kurtz S K, Perry T T. A powder technique for the evaluation of nonlinear optical materials[J]. J. Appl. Phys., 1968,39:3798-3813. doi: 10.1063/1.1656857
1. [1]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
2. [2]
  Yongjing Deng , Feiyang Li , Zijian Zhou , Mengzhu Wang , Yongkang Zhu , Jianwei Zhao , Shujuan Liu , Qiang Zhao . Chiral induction and Sb³⁺ doping in indium halides to trigger second harmonic generation and circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(8): 109085-. doi: 10.1016/j.cclet.2023.109085
3. [3]
  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
4. [4]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
5. [5]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
6. [6]
  Dong-Xue Jiao , Hui-Li Zhang , Chao He , Si-Yu Chen , Ke Wang , Xiao-Han Zhang , Li Wei , Qi Wei . Layered (C5H6ON)2[Sb2O(C2O4)3] with a large birefringence derived from the uniform arrangement of π-conjugated units. Chinese Journal of Structural Chemistry, 2024, 43(6): 100304-100304. doi: 10.1016/j.cjsc.2024.100304
7. [7]
  Dan-Ying Xing , Xiao-Dan Zhao , Chuan-Shu He , Bo Lai . Kinetic study and DFT calculation on the tetracycline abatement by peracetic acid. Chinese Chemical Letters, 2024, 35(9): 109436-. doi: 10.1016/j.cclet.2023.109436
8. [8]
  Zikang Hu , Hengjie Zhang , Zhengqiu Li , Tianbao Zhao , Zhipeng Gu , Qijuan Yuan , Baoshu Chen . Multifunctional photothermal hydrogels: Design principles, various functions, and promising biological applications. Chinese Chemical Letters, 2024, 35(10): 109527-. doi: 10.1016/j.cclet.2024.109527
9. [9]
  Qian-Qian Tang , Li-Fang Feng , Zhi-Peng Li , Shi-Hao Wu , Long-Shuai Zhang , Qing Sun , Mei-Feng Wu , Jian-Ping Zou . Single-atom sites regulation by the second-shell doping for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(9): 109454-. doi: 10.1016/j.cclet.2023.109454
10. [10]
  Chunru Liu , Ligang Feng . Advances in anode catalysts of methanol-assisted water-splitting reactions for hydrogen generation. Chinese Journal of Structural Chemistry, 2023, 42(10): 100136-100136. doi: 10.1016/j.cjsc.2023.100136
11. [11]
  Feibin Wei , Yongfang Rao , Yu Huang , Wei Wang , Hui Mei . The new challenges for the development of NH₃-SCR catalysts under new situation of energy transition in power generation industry. Chinese Chemical Letters, 2024, 35(6): 108931-. doi: 10.1016/j.cclet.2023.108931
12. [12]
  Wei Zhou , Xi Chen , Lin Lu , Xian-Rong Song , Mu-Jia Luo , Qiang Xiao . Recent advances in electrocatalytic generation of indole-derived radical cations and their applications in organic synthesis. Chinese Chemical Letters, 2024, 35(4): 108902-. doi: 10.1016/j.cclet.2023.108902
13. [13]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
14. [14]
  Ke Wang , Jia Wu , Shuyi Zheng , Shibin Yin . NiCo Alloy Nanoparticles Anchored on Mesoporous Mo2N Nanosheets as Efficient Catalysts for 5-Hydroxymethylfurfural Electrooxidation and Hydrogen Generation. Chinese Journal of Structural Chemistry, 2023, 42(10): 100104-100104. doi: 10.1016/j.cjsc.2023.100104
15. [15]
  Luyan Shi , Ke Zhu , Yuting Yang , Qinrui Liang , Qimin Peng , Shuqing Zhou , Tayirjan Taylor Isimjan , Xiulin Yang . Phytic acid-derivative Co₂B-CoPO_x coralloidal structure with delicate boron vacancy for enhanced hydrogen generation from sodium borohydride. Chinese Chemical Letters, 2024, 35(4): 109222-. doi: 10.1016/j.cclet.2023.109222
16. [16]
  Yan Zhu , Jia Liu , Meiheng Lv , Tingting Wang , Dongxiang Zhang , Rong Shang , Xin-Dong Jiang , Jianjun Du , Guiling Wang . Heavy-atom-free orthogonal configurative dye 1,7-di-anthra-aza-BODIPY for singlet oxygen generation. Chinese Chemical Letters, 2024, 35(10): 109446-. doi: 10.1016/j.cclet.2023.109446
17. [17]
  Lumin Zheng , Ying Bai , Chuan Wu . Multi-electron reaction and fast Al ion diffusion of δ-MnO₂ cathode materials in rechargeable aluminum batteries via first-principle calculations. Chinese Chemical Letters, 2024, 35(4): 108589-. doi: 10.1016/j.cclet.2023.108589

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(357)
HTML views(53)

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