Citation: Hao-Fei Ni, Jia-He Lin, Gele Teri, Qiang-Qiang Jia, Pei-Zhi Huang, Hai-Feng Lu, Chang-Feng Wang, Zhi-Xu Zhang, Da-Wei Fu, Yi Zhang. B-site ion regulation strategy enables performance optimization and multifunctional integration of hybrid perovskite ferroelectrics[J]. Chinese Chemical Letters, ;2025, 36(3): 109690. doi: 10.1016/j.cclet.2024.109690 shu

B-site ion regulation strategy enables performance optimization and multifunctional integration of hybrid perovskite ferroelectrics

Institute for Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China

zhangzhixu@zjnu.edu.cn

dawei@zjnu.edu.cn

yizhang1980@seu.edu.cn

Received Date: 7 December 2023
Revised Date: 25 January 2024
Accepted Date: 29 February 2024
Available Online: 4 March 2024

Figures(6)

The performance optimization of materials is an eternal theme and challenge in scientific research, which is reflected in ferroelectric filed to two hot topics of enhancing Curie temperature (T_C) and functional versatility. The former one vitally determines ferroelectric operational temperature range while the latter would open up new application possibilities. Effective chemical modification or doping strategies on A-site and X-site components have been successfully developed in hybrid organic-inorganic perovskite (HOIP) ferroelectrics, however, the important role of adjusting B-site ions has long been overlooked. Here, we have implemented regulation on the ion radius of the B-site component to successfully obtain two new HOIP ferroelectrics (3-pyrrolinium)BBr₃ (B = Mn and Ni). Compared to parent (3-pyrrolinium)CdBr₃, the T_C (ΔT = 99 K) was significantly optimized by replacing the Cd²⁺ with smaller Mn²⁺ or Ni²⁺ ions. More strikingly, the introduction of Mn²⁺ and Ni²⁺ ions with octahedral coordination bring out intriguing red emission and magnetism respectively, making the multifunctional integration in a single material for multiple uses. This work provides a feasible strategy for performance optimizing of HOIP ferroelectrics, and would shed light for constructing multifunctional ferroelectrics.
- Ferroelectric,
- Hybrid perovskites,
- Crystal engineering,
- Curie temperature,
- Phase transition
1. [1]
  Y. Zhao, K. Zhu, Chem. Soc. Rev. 45 (2016) 655–689. doi: 10.1039/C4CS00458B
2. [2]
  Y.M. You, W.Q. Liao, D. Zhao, et al., Science 357 (2017) 306–309. doi: 10.1126/science.aai8535
3. [3]
  W. Li, Z. Wang, F. Deschler, et al., Nat. Rev. Mater. 2 (2017) 16099. doi: 10.1038/natrevmats.2016.99
4. [4]
  Q. Jia, T. Shao, L. Tong, et al., Chin. Chem. Lett. 34 (2023) 107539. doi: 10.1016/j.cclet.2022.05.053
5. [5]
  C.F. Wang, N. Wang, C. Shi, et al., Chin. Chem. Lett. 34 (2023) 107774. doi: 10.1016/j.cclet.2022.107774
6. [6]
  Y.Y. Zhang, J.Q. Luo, Y. Han, et al., Chin. Chem. Lett. 36 (2025) 109530. doi: 10.1016/j.cclet.2024.109530
7. [7]
  M. Ksiądzyna, A. Gągor, A. Piecha-Bisiorek, et al., J. Mater. Chem. C 7 (2019) 10360–10370. doi: 10.1039/c9tc02849h
8. [8]
  M. Mączka, J.K. Zaręba, A. Gągor, et al., Chem. Mater. 33 (2021) 2331–2342. doi: 10.1021/acs.chemmater.0c04440
9. [9]
  K. Ding, H. Ye, C. Su, et al., Nat. Commun. 14 (2023) 2863. doi: 10.1038/s41467-023-38590-7
10. [10]
  W.J. Xu, P.F. Li, Y.Y. Tang, et al., J. Am. Chem. Soc. 139 (2017) 6369–6375. doi: 10.1021/jacs.7b01334
11. [11]
  B. Zhou, D. Yan, Angew. Chem. Int. Ed. 58 (2019) 15128–15135. doi: 10.1002/anie.201909760
12. [12]
  A. Kojima, K. Teshima, Y. Shirai, T. Miyasaka, J. Am. Chem. Soc. 131 (2009) 6050–6051. doi: 10.1021/ja809598r
13. [13]
  Y. Ai, R. Sun, Y.L. Zeng, et al., Chem. Sci. 12 (2021) 9742–9747. doi: 10.1039/d1sc01871j
14. [14]
  M. Rok, B. Zarychta, J. Trojan-Piegza, et al., J. Mater. Chem. C 10 (2022) 3036–3047. doi: 10.1039/d1tc05355h
15. [15]
  K. Li, Z.G. Li, J. Xu, et al., J. Am. Chem. Soc. 144 (2022) 816–823. doi: 10.1021/jacs.1c10188
16. [16]
  G.C. Schmidt, P.M. Panicker, X. Qiu, et al., Adv. Mater. 33 (2021) 2006437. doi: 10.1002/adma.202006437
17. [17]
  A. Wang, C. Zuo, X. Niu, et al., Chem. Eng. J. 451 (2023) 138926. doi: 10.1016/j.cej.2022.138926
18. [18]
  N.P. Maria Joseph Raj, N.R. Alluri, G. Khandelwal, S.J. Kim, Chem. Eng. J. 414 (2021) 128840. doi: 10.1016/j.cej.2021.128840
19. [19]
  J. Hoffman, X. Pan, J.W. Reiner, et al., Adv. Mater. 22 (2010) 2957–2961. doi: 10.1002/adma.200904327
20. [20]
  H.Y. Liu, H.Y. Zhang, X.G. Chen, R.G. Xiong, J. Am. Chem. Soc. 142 (2020) 15205–15218. doi: 10.1021/jacs.0c07055
21. [21]
  Q. Chen, H. Jiang, Y. Fan, et al., Adv. Funct. Mater. 33 (2023) 2213964. doi: 10.1002/adfm.202213964
22. [22]
  Z. Wu, W. Zhang, H. Ye, et al., J. Am. Chem. Soc. 143 (2021) 7593–7598. doi: 10.1021/jacs.1c00459
23. [23]
  S. Jiao, Z. Tang, D. Li, et al., Chem. Eng. J. 466 (2023) 143188. doi: 10.1016/j.cej.2023.143188
24. [24]
  C.C. Fan, X.B. Han, B.D. Liang, et al., Adv. Mater. 34 (2022) 2204119. doi: 10.1002/adma.202204119
25. [25]
  K. Taniguchi, M. Nishio, N. Abe, et al., Angew. Chem. Int. Ed. 60 (2021) 14350–14354. doi: 10.1002/anie.202103121
26. [26]
  C.F. Wang, H. Li, M.G. Li, et al., Adv. Funct. Mater. 31 (2021) 2009457. doi: 10.1002/adfm.202009457
27. [27]
  L. Li, X. Shang, S. Wang, et al., J. Am. Chem. Soc. 140 (2018) 6806–6809. doi: 10.1021/jacs.8b04014
28. [28]
  B. Saparov, D.B. Mitzi, Chem. Rev. 116 (2016) 4558–4596. doi: 10.1021/acs.chemrev.5b00715
29. [29]
  X.N. Hua, W.Q. Liao, Y.Y. Tang, et al., J. Am. Chem. Soc. 140 (2018) 12296–12302. doi: 10.1021/jacs.8b08286
30. [30]
  Y. Ai, H.P. Lv, Z.X. Wang, W.Q. Liao, R.G. Xiong, Trend. Chem. 3 (2021) 1088–1099. doi: 10.1016/j.trechm.2021.09.010
31. [31]
  H. Xu, F. Sun, W. Guo, et al., Angew. Chem. Int. Ed. 62 (2023) e202309416. doi: 10.1002/anie.202309416
32. [32]
  C. Ji, S. Wang, L. Li, et al., Adv. Funct. Mater. 29 (2019) 1805038. doi: 10.1002/adfm.201805038
33. [33]
  Y. Hu, L. You, B. Xu, et al., Nat. Mater. 20 (2021) 612–617. doi: 10.1038/s41563-020-00875-3
34. [34]
  X.G. Chen, Y.Y. Tang, H.P. Lv, et al., J. Am. Chem. Soc. 145 (2023) 1936–1944. doi: 10.1021/jacs.2c12306
35. [35]
  Y. Zhang, W.Q. Liao, D.W. Fu, et al., Adv. Mater. 27 (2015) 3942–3946. doi: 10.1002/adma.201501026
36. [36]
  C. Shi, L. Ye, Z.X. Gong, et al., J. Am. Chem. Soc. 142 (2020) 545–551. doi: 10.1021/jacs.9b11697
37. [37]
  Y. Ai, R. Sun, W.Q. Liao, et al., Angew. Chem. Int. Ed. 61 (2022) e202206034. doi: 10.1002/anie.202206034
38. [38]
  P.F. Li, W.Q. Liao, Y.Y. Tang, et al., J. Am. Chem. Soc. 139 (2017) 8752–8757. doi: 10.1021/jacs.7b04693
39. [39]
  H.Y. Ye, Q. Zhou, X. Niu, et al., J. Am. Chem. Soc. 137 (2015) 13148–13154. doi: 10.1021/jacs.5b08290
40. [40]
  L.E. Orgel, J. Chem. Phys. 23 (2004) 1824–1826.
41. [41]
  K.E. Lawson, J. Chem. Phys. 47 (2004) 3627–3633.
42. [42]
  T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
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2. [2]
  Zhi-Yuan Yue , Hua-Kai Li , Na Wang , Shan-Shan Liu , Le-Ping Miao , Heng-Yun Ye , Chao Shi . Dehydration-triggered structural phase transition-associated ferroelectricity in a hybrid perovskite-type crystal. Chinese Chemical Letters, 2024, 35(10): 109355-. doi: 10.1016/j.cclet.2023.109355
3. [3]
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4. [4]
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5. [5]
  Zhaohong Chen , Mengzhen Li , Jinfei Lan , Shengqian Hu , Xiaogang Chen . Organic ferroelastic enantiomers with high T_c and large dielectric switching ratio triggered by order-disorder and displacive phase transition. Chinese Chemical Letters, 2024, 35(10): 109548-. doi: 10.1016/j.cclet.2024.109548
6. [6]
  Keke Han , Wenjun Rao , Xiuli You , Haina Zhang , Xing Ye , Zhenhong Wei , Hu Cai . Two new high-temperature molecular ferroelectrics [1,5-3.2.2-Hdabcni]X (X = ClO₄⁻, ReO₄⁻). Chinese Chemical Letters, 2024, 35(6): 108809-. doi: 10.1016/j.cclet.2023.108809
7. [7]
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8. [8]
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12. [12]
  Fan Wu , Shaoyang Wu , Xin Ye , Yurong Ren , Peng Wei . Research progress of high-entropy cathode materials for sodium-ion batteries. Chinese Chemical Letters, 2025, 36(4): 109851-. doi: 10.1016/j.cclet.2024.109851
13. [13]
  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
14. [14]
  Mengjia Luo , Yi Qiu , Zhengyang Zhou . Exploring temperature-driven phase dynamics of phosphate: The periodic to incommensurately modulated long-range ordered phase transition in CsCdPO4. Chinese Journal of Structural Chemistry, 2025, 44(1): 100446-100446. doi: 10.1016/j.cjsc.2024.100446
15. [15]
  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
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  Jiarui Wu , Gengxin Wu , Yan Wang , Yingwei Yang . Crystal Engineering Based on Leaning Towerarenes. University Chemistry, 2024, 39(3): 58-62. doi: 10.3866/PKU.DXHX202304014
18. [18]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
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