Citation: Yuwei Kang, Can Yang, Jun Zhang, Qi Wu. Synergistic triple-site engineering in ABX₃-type hybrid halides for high-performance nonlinear optical crystals[J]. Chinese Chemical Letters, ;2026, 37(1): 111385. doi: 10.1016/j.cclet.2025.111385 shu

Synergistic triple-site engineering in ABX₃-type hybrid halides for high-performance nonlinear optical crystals

Yuwei Kang ^{a, b} ,
Can Yang ^a ,
Jun Zhang ^{c, *,} ,
Qi Wu ^{a, *,}

a.
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, China
b.
State Key Laboratory of Functional Crystals and Devices, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350108, China
c.
Key Laboratory of Functional Molecule Design and Interface Process, Anhui Jianzhu University, Hefei 230601, China

zhangjun@ahjzu.edu.cn

wuqi2011@whu.edu.cn

Received Date: 27 April 2025
Revised Date: 12 May 2025
Accepted Date: 28 May 2025
Available Online: 29 May 2025

Figures(4)

Achieving non-centrosymmetric (NCS) configurations in ABX₃-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn²⁺/Pb²⁺), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C₆H₁₁N₂PbCl₃ exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
- Nonlinear,
- Optical organic-inorganic hybrid,
- ABX₃ lone pair,
- Optimized balance
1. [1]
  K. Zhou, B. Qi, Z. Liu, et al., Adv. Funct. Mater. 34 (2024) 2411671. doi: 10.1002/adfm.202411671
2. [2]
  R. Tang, D. Yang, L. Ma, et al., Adv. Opt. Mater. 13 (2025) 2403044. doi: 10.1002/adom.202403044
3. [3]
  Y. Kang, C. Yang, J. Gou, et al., Inorg. Chem. 63 (2024) 2725–2731. doi: 10.1021/acs.inorgchem.3c04148
4. [4]
  W. Zeng, Y. Tian, H. Zeng, et al., Angew. Chem. Int. Ed. 64 (2025) e202422818. doi: 10.1002/anie.202422818
5. [5]
  J.J. Zhao, S.F. Li, M.H. Lv, et al., Inorg. Chem. 64 (2025) 807–812. doi: 10.1021/acs.inorgchem.4c05135
6. [6]
  H.M. Ngo, Y. Kuk, J. Lee, et al., Adv. Opt. Mater. 13 (2025) 2403241. doi: 10.1002/adom.202403241
7. [7]
  K. Liu, J. Zhao, Q. Liu, Laser Photonics Rev. 18 (2024) 2400345. doi: 10.1002/lpor.202400345
8. [8]
  Q. Zhang, R. An, X. Long, et al., Angew. Chem. Int. Ed. 64 (2025) e202415066. doi: 10.1002/anie.202415066
9. [9]
  Y. Kang, C. Yang, J. Gou, et al., Inorg. Chem. 63 (2024) 2725–2731. doi: 10.1021/acs.inorgchem.3c04148
10. [10]
  S. Cui, S. Yang, H. Wu, et al., Adv. Funct. Mater. 35 (2025) 2424059. doi: 10.1002/adfm.202424059
11. [11]
  B. Ding, X. Cheng, H. Mi, et al., Inorg. Chem. 64 (2025) 1153–1163. doi: 10.1021/acs.inorgchem.4c04869
12. [12]
  X. Kong, J. Chai, H. Zhao, et al., Inorg. Chem. Front. 12 (2025) 630–636. doi: 10.1039/d4qi02469a
13. [13]
  Y. Kang, C. Yang, J. Gou, et al., Angew. Chem. Int. Ed. 63 (2024) e202402086. doi: 10.1002/anie.202402086
14. [14]
  S. Choi, Y. Li, Y. Kuk, et al., Adv. Sci. 12 (2025) 2414503. doi: 10.1002/advs.202414503
15. [15]
  P. Li, C. Hu, F. Kong, et al., Angew. Chem. Int. Ed. 62 (2023) e202301420. doi: 10.1002/anie.202301420
16. [16]
  J.H. Wu, C.L. Hu, Y.F. Li, et al., Chem. Sci. 15 (2024) 8071–8079. doi: 10.1039/d4sc01716a
17. [17]
  R. Tang, C. Hu, B. Wu, et al., Angew. Chem. Int. Ed. 58 (2019) 15358–15361. doi: 10.1002/anie.201909735
18. [18]
  S. Liu, L. He, Y. Wang, et al., Chin. Chem. Lett. 33 (2022) 1032–1036. doi: 10.1016/j.cclet.2021.07.039
19. [19]
  Y. Hu, X. Jiang, C. Wu, et al., Chem. Mater. 33 (2021) 5700–5708. doi: 10.1021/acs.chemmater.1c01434
20. [20]
  K. Liu, J. Zhao, Q. Liu, Laser Photonics Rev. 18 (2024) 2400345. doi: 10.1002/lpor.202400345
21. [21]
  S. Yang, H. Wu, Z. Hu, et al., Inorg. Chem. 63 (2024) 1404–1413. doi: 10.1021/acs.inorgchem.3c03928
22. [22]
  Y. Li, J. Luo, S. Zhao, Acc. Chem. Res. 55 (2022) 3460–3469. doi: 10.1021/acs.accounts.2c00542
23. [23]
  F. Chen, H. Wu, Z. Hu, et al., Chem. Sci. 16 (2025) 2015–2023. doi: 10.1039/d4sc05747c
24. [24]
  W. Han, P. Cheng, J. Guan, et al., Angew. Chem. Int. Ed. 16 (2025) e202500786.
25. [25]
  J.W. Lee, S. Tan, S.I. Seok, et al., Science 375 (2022) eabj1186. doi: 10.1126/science.abj1186
26. [26]
  L. Zhou, P.P. Shi, X.M. Liu, et al., NPG Asia Mater. 11 (2019) 1–9. doi: 10.1038/s41427-018-0100-z
27. [27]
  L. He, Y. Liu, P. Shi, et al., ACS Appl. Mater. Interfaces 12 (2020) 53799–53806. doi: 10.1021/acsami.0c16180
28. [28]
  Y. Liu, Y. Gong, S. Geng, et al., Angew. Chem. Int. Ed. 61 (2022) e202208875. doi: 10.1002/anie.202208875
29. [29]
  Y. Zheng, J. Xu, X. Bu, Adv. Opt. Mater. 10 (2022) 2101545. doi: 10.1002/adom.202101545
30. [30]
  D. Chen, S. Hao, L. Fan, et al., Chem. Mater. 33 (2021) 8106–8111. doi: 10.1021/acs.chemmater.1c02896
31. [31]
  Q. Shui, H. Tang, R. Fu, et al., Angew. Chem. Int. Ed. 60 (2021) 2116–2119. doi: 10.1002/anie.202013088
32. [32]
  J. Guan, Y. Zheng, P. Cheng, et al., J. Am. Chem. Soc. 145 (2023) 26833–26842. doi: 10.1021/jacs.3c09395
33. [33]
  P. Kubelka, F. Munk, Z. Tech. Phys. 12 (1931) 259–274.
34. [34]
  C.C. Stoumpos, L. Frazer, D.J. Clark, et al., J. Am. Chem. Soc. 137 (2015) 6804–6819. doi: 10.1021/jacs.5b01025
35. [35]
  M. Mittal, A. Jana, S. Sarkar, et al., J. Phys. Chem. Lett. 7 (2016) 3270–3277. doi: 10.1021/acs.jpclett.6b01406
36. [36]
  Y. Deng, X. Dong, M. Yang, et al., Dalton Trans. 48 (2019) 17451–17455. doi: 10.1039/c9dt04102h
37. [37]
  S. Kurtz, T. Perry, J. Appl. Phys. 39 (1968) 3798–3813. doi: 10.1063/1.1656857
38. [38]
  M.D. Segall, P.J.D. Lindan, M.J. Probert, et al., J. Phys. Condens Mat. 14 (2002) 2717–2744. doi: 10.1088/0953-8984/14/11/301
39. [39]
  V. Milman, B. Winkler, J.A. White, et al., Int. J. Quantum Chem. 77 (2000) 895–910. doi: 10.1002/(SICI)1097-461X(2000)77:5<895::AID-QUA10>3.0.CO;2-C
40. [40]
  J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865–3868. doi: 10.1103/PhysRevLett.77.3865
1. [1]
  Miao-Bin Xu , Qian-Qian Chen , Bing-Xuan Li , Ke-Zhao Du , Jin Chen . π-Lone pair synergy in (C₇H₄NO₄)(IO₃): Optimal balance among SHG, birefringence, and bandgap performance. Chinese Chemical Letters, 2025, 36(11): 110513-. doi: 10.1016/j.cclet.2024.110513
2. [2]
  Le Ye , Wei-Xiong Zhang . Structural phase transition in a new organic-inorganic hybrid post-perovskite: (N,N-dimethylpyrrolidinium)[Mn(N(CN)2)3]. Chinese Journal of Structural Chemistry, 2024, 43(6): 100257-100257. doi: 10.1016/j.cjsc.2024.100257
3. [3]
  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
4. [4]
  Hongyuan Sha , Dongling Yang , Yanran Shang , Zujian Wang , Rongbing Su , Chao He , Xiaoming Yang , Xifa Long . Trithionic guanidine: A novel semi-organic short-wave ultraviolet nonlinear optical sulfate with dimeric heteroleptic tetrahedra. Chinese Chemical Letters, 2025, 36(4): 109730-. doi: 10.1016/j.cclet.2024.109730
5. [5]
  Yan Cheng , Hai-Quan Yao , Ya-Di Zhang , Chao Shi , Heng-Yun Ye , Na Wang . Nitrate-bridged hybrid organic-inorganic perovskites. Chinese Journal of Structural Chemistry, 2024, 43(9): 100358-100358. doi: 10.1016/j.cjsc.2024.100358
6. [6]
  Ruiyan CHEN , Yanping HE , Jian ZHANG . Synthesis and third-order nonlinear optical property of Ti₄L₆ cage-based metal-organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2149-2156. doi: 10.11862/CJIC.20250177
7. [7]
  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
8. [8]
  Lihua Gao , Yinglei Han , Chensheng Lin , Huikang Jiang , Guang Peng , Guangsai Yang , Jindong Chen , Ning Ye . Halogen-assisted octet binding electrons construction of pnictogens towards wide-bandgap nonlinear optical pnictides. Chinese Chemical Letters, 2024, 35(12): 109529-. doi: 10.1016/j.cclet.2024.109529
9. [9]
  Kangrong Yan , Ziqiu Shen , Yanchun Huang , Benfang Niu , Hongzheng Chen , Chang-Zhi Li . Curing the vulnerable heterointerface via organic-inorganic hybrid hole transporting bilayers for efficient inverted perovskite solar cells. Chinese Chemical Letters, 2024, 35(6): 109516-. doi: 10.1016/j.cclet.2024.109516
10. [10]
  Ting Shi , Ziyang Song , Yaokang Lv , Dazhang Zhu , Ling Miao , Lihua Gan , Mingxian Liu . Hierarchical porous carbon guided by constructing organic-inorganic interpenetrating polymer networks to facilitate performance of zinc hybrid supercapacitors. Chinese Chemical Letters, 2025, 36(1): 109559-. doi: 10.1016/j.cclet.2024.109559
11. [11]
  Weihong Ding , Kaiyue Song , Xianglong Li , Xiaoxia Sun . High-temperature-stable RRAMs with well-defined thermal effect mechanisms enable by engineering of robust 2D <100>-oriented organic-inorganic hybrid perovskites. Chinese Chemical Letters, 2025, 36(4): 110495-. doi: 10.1016/j.cclet.2024.110495
12. [12]
  Kai Han , Guohui Dong , Ishaaq Saeed , Tingting Dong , Chenyang Xiao . Morphology and photocatalytic tetracycline degradation of g-C3N4 optimized by the coal gangue. Chinese Journal of Structural Chemistry, 2024, 43(2): 100208-100208. doi: 10.1016/j.cjsc.2023.100208
13. [13]
  Jieqiong Xu , Wenbin Chen , Shengkai Li , Qian Chen , Tao Wang , Yadong Shi , Shengyong Deng , Mingde Li , Peifa Wei , Zhuo Chen . Organic stoichiometric cocrystals with a subtle balance of charge-transfer degree and molecular stacking towards high-efficiency NIR photothermal conversion. Chinese Chemical Letters, 2024, 35(10): 109808-. doi: 10.1016/j.cclet.2024.109808
14. [14]
  Yongmei Xia , Zuming He , Gang He , Lianxiang Chen , Juan Zhang , Jiangbin Su , Muhammad Saboor Siddique , Xiaofei Fu , Guihua Chen , Wei Zhou . Lead-free perovskite Cs₃Bi₂Br₉/FeS₂ hollow core-shell Z-scheme heterojunctions toward optimized photothermal-photocatalytic H₂ production. Chinese Chemical Letters, 2025, 36(10): 111521-. doi: 10.1016/j.cclet.2025.111521
15. [15]
  Chong Liu , Ling Li , Jiahui Gao , Yanwei Li , Nazhen Zhang , Jing Zang , Cong Liu , Zhaopei Guo , Yanhui Li , Huayu Tian . The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance. Chinese Chemical Letters, 2025, 36(2): 110118-. doi: 10.1016/j.cclet.2024.110118
16. [16]
  Yan Chen , Xinnan Wang , Yifan Lin , Chun Liu . Shape/dimension-controllable organic heterostructures from one monomer pair. Chinese Chemical Letters, 2025, 36(3): 109903-. doi: 10.1016/j.cclet.2024.109903
17. [17]
  Xilin Bai , Wei Deng , Jingjuan Wang , Ming Zhou . Enrichment-enhanced detection strategy in the optimized monitoring system of dopamine with carbon dots-based probe. Chinese Chemical Letters, 2025, 36(2): 109959-. doi: 10.1016/j.cclet.2024.109959
18. [18]
  Quanyou Guo , Yue Yang , Tingting Hu , Hongqi Chu , Lijun Liao , Xuepeng Wang , Zhenzi Li , Liping Guo , Wei Zhou . Regulating local electron transfer environment of covalent triazine frameworks through F, N co-modification towards optimized oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(1): 110235-. doi: 10.1016/j.cclet.2024.110235
19. [19]
  Qin Wang , Han Luo , Luli Wang , Ling Huang , Liling Cao , Xuehua Dong , Guohong Zou . KSb₂F₇·2KNO₃: Unveiling the peak birefringence in inorganic antimony oxysalts. Chinese Chemical Letters, 2025, 36(7): 110173-. doi: 10.1016/j.cclet.2024.110173
20. [20]
  Jing JIN , Zhuming GUO , Zhiyin XIAO , Xiujuan JIANG , Yi HE , Xiaoming LIU . Tuning the stability and cytotoxicity of fac-[Fe(CO)₃I₃]^- anion by its counter ions: From aminiums to inorganic cations. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 991-1004. doi: 10.11862/CJIC.20230458

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(8)
HTML views(1)

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

Synergistic triple-site engineering in ABX3-type hybrid halides for high-performance nonlinear optical crystals

Metrics

通讯作者: 陈斌, bchen63@163.com

Synergistic triple-site engineering in ABX₃-type hybrid halides for high-performance nonlinear optical crystals