Citation: Chen Sa, Shang Ran, Wang Bingwu, Wang Zheming, Gao Song. An Anisotropic Diluted Magnetic Hybrid Perovskite Series of [CH₃NH₃][Co_xZn_1-x(HCOO)₃][J]. Acta Physico-Chimica Sinica, ;2020, 36(1): 190701. doi: 10.3866/PKU.WHXB201907012 shu

An Anisotropic Diluted Magnetic Hybrid Perovskite Series of [CH₃NH₃][Co_xZn_1-x(HCOO)₃]

Beijing National Laboratory for Molecular Sciences, Beijing Key Laboratory of Magnetoelectric Materials and Devices, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Corresponding author: Wang Zheming, zmw@pku.edu.cn Gao Song, gaosong@pku.edu.cn
Received Date: 1 July 2019
Revised Date: 5 September 2019
Accepted Date: 6 September 2019
Available Online: 20 January 2019
Fund Project: the National Natural Science Foundation of China 21671008the National Natural Science Foundation of China 21621061The project was supported by the National Natural Science Foundation of China (21671008, 21621061) and the National Key Basic Research Program of China (2018YFA0306003)the National Key Basic Research Program of China 2018YFA0306003

Inorganic-organic or hybrid perovskite materials, which are the complementary counterparts of pure inorganic perovskites, can provide many new opportunities in the researches of phase transitions, critical phenomena, and relevant properties, as they combine the characteristics of inorganic and organic components. Therefore, the hybrid perovskites of ammonium metal formate framework are very promising, and their properties have been found to be strongly dependent on the characteristics of the constituent metal ions and/or ammonium ions. Herein, we used solid solution strategies, borrowed from solid state chemistry, to investigate the anisotropic diluted magnetic hybrid perovskite system of [CH₃NH₃][Co_xZn_1-x(HCOO)₃], wherein the B-sites are occupied by the mixed metal ions of Co²⁺ and Zn²⁺. The solid solution compounds of this series in the range x = 0–1 (or the molar percent Co% = 0–100%) were successfully prepared using conventional solution chemistry methods. The resulting compounds were demonstrated to be iso-structural by using both single-crystal and powder X-ray diffraction analyses. The solid solution crystals belong to the orthorhombic space group Pnma, with the cell parameters being a = 8.3015(2)–8.3207(3) Å, b = 11.6574(4)–11.6811(5) Å, c = 8.1315(3)–8.1427(4) Å, and V = 787.89(5)–790.98(7) Å³. The perovskite structure consists of a simple cubic anionic metal-formate framework and CH₃NH₃⁺ cations which are located in the framework cavities, with N―H···O hydrogen bonds formed between the framework and the cation. The members of this series showed negligible changes (< 0.4%) in their respective lattice and structural parameters. Thus, the prepared solid solution compounds constitute good molecule-based examples for the study of magnetic dilution under almost the same structural parameters and molecular geometries. Upon dilution, the magnetization per mole of Co at low temperatures and low fields was suppressed by the magnetic anisotropy of Co²⁺ and gradual destruction of the large spin canting between coupled Co²⁺ ions, in contrast to the magnetization enhancement observed in the isotropic diluted system of [CH₃NH₃][Mn_xZn_1-x(HCOO)₃] with the same perovskite structure. The percolation limit was estimated as (Co%)_P = 27(1)% (or x_P = 0.27(1)) from the magnetic data, which was slightly lower than that predicted by the percolation theory for a simple cubic lattice (31%); this trend was due to the strong magnetic anisotropy of the present system. In addition, rare incommensurate phase transitions were primarily detected below ~120 K for the pure Co and Zn members, which may also affect the magnetic properties of the materials.
- Hybrid perovskite,
- Ammonium metal formate framework,
- Magnetic dilution,
- Structure,
- Magnetism
1. [1]
  (a) Wang, Z. L.; Wang, Z. C. Functional and Smart Materials – Structural Evolution and Structural Analysis; Plenum Press: New York, 1998.
  (b) Müller, K. A.; Kool, T. W. Properties of Perovskites and Other Oxides; World Scientific Publishing Co. Pte. Ltd.: London, 2010.
2. [2]
  (a) Saparov, B.; Mitzi, D. B. Chem. Rev. 2016, 116, 4558. doi: 10.1021/acs.chemrev.5b00715
  (b) Mitzi, D. B. Prog. Inorg. Chem. 1999, 48, 1. doi: 10.1002/9780470166499.ch1
  (c) Li, W.; Wang, Z. M.; Deschler, F.; Gao, S.; Friend, R. H.; Cheetham, A. K. Nat. Rev. Mater. 2017, 2, 16099. doi: 10.1038/natrevmats.2016.99
  (d) Xu, W. J.; Du, Z. Y.; Zhang, W. X.; Chen, X. M. CrystEngComm 2016, 18, 7915. doi: 10.1039/c6ce01485b
3. [3]
  (a) Shang, R.; Chen, S.; Wang, Z. M.; Gao, S. Functional Magnetic Materials Based on Metal Formate Frameworks. In Metal-Organic Framework Materials; Macgillivray, L. R., Lukehart, C. M. Eds; John Wiley & Sons, Ltd.: Chichester, 2014. doi: 10.1002/9781119951438.eibc2215
  (b) Wang, Z. M.; Hu, K. L.; Gao, S.; Kobayashi, H. Adv. Mater. 2010, 22, 1526. doi: 10.1002/adma.200904438
4. [4]
  (a) Wang, Z. M.; Zhang, B.; Otsuka, T.; Inoue, K.; Kobayashi, H.; Kurmoo, M. Dalton Trans. 2004, 2209. doi: 10.1039/b404466e
  (b) Wang, X. Y.; Gan, L.; Zhang, S. W.; Gao, S. Inorg. Chem. 2004, 43, 4615. doi: 10.1021/ic0498081
  (c) Hu, K. L.; Kurmoo, M.; Wang, Z. M.; Gao, S. Chem. Eur. J. 2009, 15, 12050. doi: 10.1002/chem.200901605
5. [5]
  (a) Chen, S.; Shang, R.; Hu, K. L.; Wang, Z. M.; Gao, S. Inorg. Chem. Front. 2014, 1, 83. doi: 10.1039/c3qi00034f
  (b) Kieslich, G.; Kumagai, S.; Butler, K. T.; Okamura, T.; Hendon, C. H.; Sun, S.; Yamashita, M.; Walshd, A.; Cheetham, A. K. Chem. Commun. 2015, 51, 15538. doi: 10.1039/c5cc06190c
  (c) Kieslich, G.; Forse, A. C.; Sun, S.; Butler, K. T.; Kumagai, S.; Wu, Y.; Warren, M. R.; Walsh, A.; Grey, C. P.; Cheetham, A. K. Chem. Mater. 2016, 28, 312. doi: 10.1021/acs.chemmater.5b04143
6. [6]
  (a) Gómez-Aguirre, L. C.; Pato-Doldán, B.; Mira, J.; Castro-García, S.; Señarís-Rodríguez, M. A.; Sánchez-Andújar, M.; Singleton, J.; Zapf, V. S. J. Am. Chem. Soc. 2016, 138, 1122. doi: 10.1021/jacs.5b11688
  (b) Fu, D. W.; Zhang, W.; Cai, H. L.; Zhang, Y.; Ge, J. Z.; Xiong, R. G.; Huang, S. D.; Nakamura, T. Angew. Chem. Int. Ed. 2011, 50, 11947. doi: 10.1002/anie.201103265
  (c) Jain, P.; Ramachandran, V.; Clark, R. J.; Zhou, H. D.; Toby, B. H.; Dalal, N. S.; Kroto, H. W.; Cheetham, A. K. J. Am. Chem. Soc. 2009, 131, 13625. doi: 10.1021/ja904156s
  (d) Mączka, M.; Gągor, A.; Ptak, M.; Paraguassu, W. T.; da Silva, A.; Sieradzki, A.; Pikul, A. Chem. Mater. 2017, 29, 2264. doi: 10.1021/acs.chemmater.6b05249
7. [7]
  (a) Yu, Y.; Shang, R.; Chen, S.; Wang, B. W.; Wang, Z. M.; Gao, S. Chem. Eur. J. 2017, 23, 9857. doi: 10.1002/chem.201701099
  (b) Mączka, M.; Pietraszko, A.; Macalik, L.; Sieradzki, A.; Trzmiel, J.; Pikul, A. Dalton Trans. 2014, 43, 17075. doi: 10.1039/c4dt02586e
  (c) Mączka, M.; Bondzior, B.; Dereń, P.; Sieradzki, A.; Trzmiel, J.; Pietraszko, A.; Hanuza, J. Dalton Trans. 2015, 44, 6871. doi: 10.1039/c5dt00060b
  (d) Ptak, M.; Mączka, M.; Gągor, A.; Sieradzki, A.; Stroppa, A.; Di Sante, D.; Perez-Mato, J. M.; Macalik, L. Dalton Trans. 2016, 45, 2574. doi: 10.1039/c5dt04536c
  (e) Ptak, M.; Mączka, M.; Gągor, A.; Sieradzki, A.; Bondzior, B.; Dereń, P.; Pawlus, S. Phys. Chem. Chem. Phys. 2016, 18, 29629. doi: 10.1039/c6cp05151k
8. [8]
  (a) Chen, S.; Shang, R.; Wang, B. W.; Wang, Z. M.; Gao, S. Angew. Chem. Int. Ed. 2015, 54, 11093. doi: 10.1002/anie.201504396
  (b) Kieslich, G.; Kumagai, Sh.; Forse, A. C.; Sun, S.; Henke, S.; Yamashita, M.; Greyd, C. P.; Cheetham, A. K. Chem. Sci. 2016, 7, 5108. doi: 10.1039/c6sc01247g
9. [9]
  (a) Evans, N. L.; Thygesen, P. M. M.; Boströ m, H. L. B.; Reynolds, E. M.; Collings, I. E.; Phillips, A. E.; Goodwin, A. L. J. Am. Chem. Soc. 2016, 138, 9393. doi: 10.1021/jacs.6b05208
  (b) Shang, R.; Sun, X.; Wang, Z. M.; Gao, S. Chem. Asian J. 2012, 7, 1697. doi: 10.1002/asia.201200139
10. [10]
  (a) Chen, S. Ammonium-Metal-Formate Perovskites: Coexistence and Manipulation of Magnetic and Electric Ordering. Ph. D. Dissertation, Peking University, Beijing, 2016.
  (b) Yu, Y. The Study on the Functional Materials of Heterometallic Ammonium Metal Formates. Ph. D. Dissertation, Peking University, Beijing, 2017.
11. [11]
  (a) de Jongh, L. J. Static Thermodynamic Properties of Site-Random Magnetic Systems and Percolation Problem. In Magnetic Phase Transitions - Proceedings of a Summer School; Ausloos, M., Elliott R. J. Eds.; Springer-Verlag: Berlin Heidelberg, 1983; pp. 172-194.
  (b) Binder, K.; Kob, W. Glassy Materials and Disordered Solids – An Introduction to Their Statictical Mechanics; World Scientific Publishing Co. Pte. Ltd.: Singapore, 2005.
  (c) Zallen, R. The Physics of Amorphous Solids; Wiley: New York, 1983.
12. [12]
  CrysAlisPro software, Rigaku Oxford Diffraction: Tokyo, Japan, 2015.
13. [13]
  Sheldrick, G. M. SHELX-97, Program for Crystal Structure Determination, University of Göttingen, Germany, 1997.
14. [14]
  Mulay, L. N.; Boudreaux, E. A. Theory and Applications of Molecular Diamagnetism; John Wiley & Sons Inc.: New York, 1976.
15. [15]
  Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds; Wiley: New York, 1986.
16. [16]
  (a) Mączka, M.; Ciupa, A.; Gągor, A.; Sieradzki, A.; Pikul, A.; Macalik, B.; Drozd, M. Inorg. Chem. 2014, 53, 5260. doi: 10.1021/ic500479e
  (b) Mączka, M.; Ptak, M.; Macalik, L. Vib. Spectrosc. 2014, 71, 98. doi: 10.1016/j.vibspec.2014.01.013
  (c) Mączka, M.; Szymborska-Małek, K.; Ciupa, A.; Hanuza, J. Vib. Spectrosc. 2015, 77, 17. doi: 10.1016/j.vibspec.2015.02.003
17. [17]
  (a) van Smaalen, S. Incommensurate Crystallography; Oxford University Press Inc.: New York, 2007.
  (b) Janssen, T.; Chapuis, G.; de Boissieu, M. Aperiodic Crystals: from Modulated Phases to Quasicrystals; Oxford University Press Inc.: New York, 2007.
18. [18]
  Chen, S.; Shang, R.; Wang, B. W. Wang, Z. M.; Gao, S. APL Mater. 2018, 6, 114205. doi: 10.1063/1.5040688 doi: 10.1063/1.5040688
19. [19]
  Carlin, R. L.; van Duyneveldt, A. J. Magnetic Properties of Transition Metal Compounds; Springer-Verlag: New York, 1977.
20. [20]
  (a) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353. doi: 10.1039/b804757j
  (b) Lloret, F.; Julve, M.; Cano, J.; Ruiz-García, R.; Pardo, E. Inorg. Chim. Acta 2008, 361, 3432. doi: 10.1016/j.ica.2008.03.114
  (c) Palii, A. V.; Tsukerblat, B. S.; Coronado, E.; Clemente-Juan, J. M.; Borras-Almenar, J. J. Inorg. Chem. 2003, 42, 2455. doi: 10.1021/ic0259686
21. [21]
  Boča, M.; Svoboda, I.; Renz, F.; Fuess, H. Acta Cryst. C. 2004, 60, m631. doi: 10.1107/s0108270104025776 doi: 10.1107/s0108270104025776
22. [22]
  Casey, A. T.; Mitra, S. Magnetic Behavior of Components Containing dⁿ Ions. In Theory and Application of Molecular Paramagnetism; Mulay, L. N., Boudreaux, E. A. Eds; Wiley: New York, 1976; pp. 211-215.
23. [23]
  (a) Breed, D. J.; Gilijamse, K.; Sterkenburg, J. W. E.; Miedema, A. R. J. Appl. Phys. 1970, 41, 1267. doi: 10.1063/1.1658906
  (b) Harris, A. B.; Kirkpatrick, S. Phys. Rev. B 1977, 16, 542. doi: 10.1103/physrevb.16.542
  (c) King, A. R.; Jaccarino, V. J. Appl. Phys. 1981, 52, 1785. doi: 10.1063/1.329714
24. [24]
  Manaka, H.; Nagata, S.; Watanabe, Y.; Kikunaga, K.; Yamamoto, T.; Terada, N.; Obara, K. J. Phys.: Conf. Ser. 2009, 145, 012080. doi: 10.1088/1742-6596/145/1/012080 doi: 10.1088/1742-6596/145/1/012080
25. [25]
  (a) Christensen, K.; Moloney, N. R. Complexity and Criticality; Imperial College Press: London, 2005.
  (b) Stinchcombe, R. B. J. Phys. C: Solid State Phys. 1979, 12, 4533. doi: 10.1088/0022-3719/12/21/020
  (c) Sur, A.; Lebowitz, J. L.; Marro, J.; Kalos, M. H.; Kirkpatrick, S. J. Statis. Phys. 1976, 15, 345. doi: 10.1007/bf01020338
26. [26]
  (a) Enoki, T.; Tsujikawa, I. J. Phys. Soc. Japan 1975, 39, 324. doi: 10.1143/jpsj.39.324
  (b) Elliott, R. J.; Heap, B. R. Proc. R. Soc. London. Ser. A 1962, 265, 264. doi: 10.1098/rspa.1962.0008
1. [1]
  Yan Cheng , Hua-Peng Ruan , Yan Peng , Longhe Li , Zhenqiang Xie , Lang Liu , Shiyong Zhang , Hengyun Ye , Zhao-Bo Hu . Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et₃NCH₂Cl]₂[MnBr₄]. Chinese Chemical Letters, 2024, 35(4): 108554-. doi: 10.1016/j.cclet.2023.108554
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]
  Dongying Fu , Lin Pan , Yanli Ma , Yue Zhang . Bilayered Dion–Jacobson lead-iodine hybrid perovskite with aromatic spacer for broadband photodetection. Chinese Chemical Letters, 2025, 36(2): 109621-. doi: 10.1016/j.cclet.2024.109621
4. [4]
  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
5. [5]
  Qiuyu Ming , Huijun Jiang , Zhihao Zhang . A Sightseeing Tour of Folic Acid Processing Plant. University Chemistry, 2024, 39(9): 11-15. doi: 10.12461/PKU.DXHX202404092
6. [6]
  Yueyue WEI , Xuehua SUN , Hongmei CHAI , Wanqiao BAI , Yixia REN , Loujun GAO , Gangqiang ZHANG , Jun ZHANG . Two Ln-Co (Ln=Eu, Sm) metal-organic frameworks: Structures, magnetism, and fluorescent sensing sulfasalazine and glutaraldehyde. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2475-2485. doi: 10.11862/CJIC.20240193
7. [7]
  Xiaoling WANG , Hongwu ZHANG , Daofu LIU . Synthesis, structure, and magnetic property of a cobalt(Ⅱ) complex based on pyridyl-substituted imino nitroxide radical. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 407-412. doi: 10.11862/CJIC.20240214
8. [8]
  Xiaxia LIU , Xiaofang MA , Luxia GUO , Xianda HAN , Sisi FENG . Structure and magnetic properties of Mn(Ⅱ) coordination polymers regulated by N-auxiliary ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 587-596. doi: 10.11862/CJIC.20240269
9. [9]
  Zhaodong WANG . In situ synthesis, crystal structure, and magnetic characterization of a trinuclear copper complex based on a multi-substituted imidazo[1,5-a]pyrazine scaffold. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 597-604. doi: 10.11862/CJIC.20240268
10. [10]
  Yadan SUN , Xinfeng LI , Qiang LIU , Oshio Hiroki , Yinshan MENG . Structures and magnetism of dinuclear Co complexes based on imine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2212-2220. doi: 10.11862/CJIC.20240131
11. [11]
  Ning Zhang , Mengjie Qin , Jiawen Zhu , Xuejing Lou , Xiao Tian , Wende Ma , Youmei Wang , Minghua Lu , Zongwei Cai . Thickness-controllable synthesis of metal-organic framework based hollow nanoflowers with magnetic core via liquid phase epitaxy for phosphopeptides enrichment. Chinese Chemical Letters, 2025, 36(4): 110177-. doi: 10.1016/j.cclet.2024.110177
12. [12]
  Shenhao QIU , Qingquan XIAO , Huazhu TANG , Quan XIE . First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2250-2258. doi: 10.11862/CJIC.20240104
13. [13]
  Run-Han Li , Tian-Yi Dang , Wei Guan , Jiang Liu , Ya-Qian Lan , Zhong-Min Su . Evolution exploration and structure prediction of Keggin-type group IVB metal-oxo clusters. Chinese Chemical Letters, 2024, 35(5): 108805-. doi: 10.1016/j.cclet.2023.108805
14. [14]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
15. [15]
  Ziyi Liu , Xunying Liu , Lubing Qin , Haozheng Chen , Ruikai Li , Zhenghua Tang . Alkynyl ligand for preparing atomically precise metal nanoclusters: Structure enrichment, property regulation, and functionality enhancement. Chinese Journal of Structural Chemistry, 2024, 43(11): 100405-100405. doi: 10.1016/j.cjsc.2024.100405
16. [16]
  Changyuan Bao , Yunpeng Jiang , Haoyin Zhong , Huaizheng Ren , Junhui Wang , Binbin Liu , Qi Zhao , Fan Jin , Yan Meng Chong , Jianguo Sun , Fei Wang , Bo Wang , Ximeng Liu , Dianlong Wang , John Wang . Synergizing 3D-printed structure and sodiophilic interface enables highly efficient sodium metal anodes. Chinese Chemical Letters, 2024, 35(11): 109353-. doi: 10.1016/j.cclet.2023.109353
17. [17]
  Na Wang , Wang Luo , Huaiyi Shen , Huakai Li , Zejiang Xu , Zhiyuan Yue , Chao Shi , Hengyun Ye , Leping Miao . Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system. Chinese Chemical Letters, 2024, 35(5): 108696-. doi: 10.1016/j.cclet.2023.108696
18. [18]
  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
19. [19]
  Tian Yang , Yi Liu , Lina Hua , Yaoyao Chen , Wuqian Guo , Haojie Xu , Xi Zeng , Changhao Gao , Wenjing Li , Junhua Luo , Zhihua Sun . Lead-free hybrid two-dimensional double perovskite with switchable dielectric phase transition. Chinese Chemical Letters, 2024, 35(6): 108707-. doi: 10.1016/j.cclet.2023.108707
20. [20]
  Xiao-Tong Sun , Hao-Fei Ni , Yi Zhang , Da-Wei Fu . Hybrid perovskite shows temperature-dependent photoluminescence and dielectric response triggered by halogen substitution. Chinese Journal of Structural Chemistry, 2024, 43(6): 100212-100212. doi: 10.1016/j.cjsc.2023.100212

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(209)
HTML views(23)

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

An Anisotropic Diluted Magnetic Hybrid Perovskite Series of [CH3NH3][CoxZn1-x(HCOO)3]

Metrics

通讯作者: 陈斌, bchen63@163.com

An Anisotropic Diluted Magnetic Hybrid Perovskite Series of [CH₃NH₃][Co_xZn_1-x(HCOO)₃]