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Two-dimensional mixed tetrahedral–octahedral hybrid perovskites with coexisting ferroelectricity and intralayer antiferromagnetism

Nature Synthesis volume 5, pages 445–454 (2026)Cite this article

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Abstract

The mixed tetrahedral–octahedral (MTO) architecture, a characteristic structural motif of brownmillerite and spinel oxides, underpins the multiferroic behaviour and magnetoelectric coupling exhibited by these oxides. Yet, this structural motif remains unexplored in two-dimensional hybrid organic–inorganic perovskites (HOIPs) that typically adopt the octahedral framework. Here we demonstrate that incorporating sterically demanding organic ligands into copper halide HOIPs stabilizes the MTO phase over the Ruddlesden–Popper phase during single-crystal growth. This approach yields a family of MTO perovskites exhibiting structural asymmetry and diverse magnetic orderings. Interestingly, (4,4-difluoropiperidinium)2CuBr4 displays concurrent ferroelectricity and intralayer antiferromagnetism. By monitoring strain-mediated phase evolution, we examine the reversible transition between the MTO and Ruddlesden–Popper phases. Our work broadens the structural diversity of 2D HOIP beyond conventional octahedral frameworks, establishing a framework for exploring emergent multiferroicity and magnetoelectric phenomena.

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Fig. 1: Design strategy for 2D MTO perovskites.
Fig. 2: Crystal structures and magnetic configurations of 2D MTO copper bromide perovskites.
Fig. 3: Ferroelectricity in DFPP2CuBr4.
Fig. 4: Intralayer AFM in DFPP2CuBr4.
Fig. 5: Strain-driven phase transition between the RP and MTO phases.

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Data availability

All data supporting the findings of this study are available in the article and its Supplementary Information. Source data are provided with this paper. The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers DFPR2CuBr4 (CCDC 2350516, 2454190, 2428613), DFPP2CuBr4 (CCDC 2350517), DFAZ2CuBr4·0.5H2O (CCDC 2375732), DFAT2CuBr4 (CCDC 2350515), DFPP2CuCl4 (CCDC 2428842) and (R-3FP)2CuCl4 (CCDC 2429039, 2429040). These data can be obtained free of charge via The Cambridge Crystallographic Data Centre at www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

K.P.L. acknowledges funding support from Hong Kong’s Research Grants Council GRF project ID P0046892 (funding reference 1530223) and HK PolyU’s grant no. P0043087, as well as Singapore’s Ministry of Education Tier 1 Grant ‘A new class of 2D metal free dielectric’ grant no. A80026710000. W.H. acknowledges the support by the National Key R&D Program (2022YFB3603800, 2022YFA1204401, 2021YFB3600700), the National Natural Science Foundation of China (52121002, U21A6002). High-pressure XRD data were collected at beamline station BL15U1 (31124.02.SSRF.BL15U1) of Shanghai Synchrotron Radiation Facility (SSRF, 31124.02.SSRF), Shanghai, China.

Author information

Author notes

  1. These authors contributed equally: Ming Wang, Shurong Yuan, Dequan Jiang.

Authors and Affiliations

  1. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Ming Wang, Chuanqi Zhang, Wenping Hu & Kian Ping Loh

  2. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Ming Wang, Walter P. D. Wong, Hengxing Yang, Chuanqi Zhang & Kian Ping Loh

  3. Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong SAR, China

    Shurong Yuan, Hwa Seob Choi & Kian Ping Loh

  4. School of Materials Science and Engineering, Peking University, Beijing, China

    Dequan Jiang & Yonggang Wang

  5. Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden

    Walter P. D. Wong

  6. State Key Laboratory of Advanced Materials for Intelligent Sensing, Key Laboratory of Organic Integrated Circuit, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, Tianjin University & Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, China

    Xiaotao Zhang & Wenping Hu

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Contributions

The work was conceived by M.W., S.Y., D.J., W.H. and K.P.L. with input from all authors. M.W. carried out the synthesis, single-crystal XRD, PFM and P–E curve characterizations. S.Y. performed DFT calculations and analysed the results. D.J. performed the DAC experiment under the supervision of Y.W. W.P.D.W. and H.Y. analysed the single-crystal XRD data. H.S.C. performed variable-temperature XRD. C.Z. conducted non-contact atomic force microscope. X.Z. helped to measure the magnetic properties. W.H. and K.P.L. supervised this project. M.W. and K.P.L. cowrote the paper.

Corresponding authors

Correspondence to Wenping Hu or Kian Ping Loh.

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The authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Linn Leppert and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Materials and conventional methods; Supplementary Notes 1 and 2, Figs. 1–28 and Tables 1–6; and X-ray structures.

Supplementary Data 1

Crystallographic data for compound DFPR2CuBr4 at room temperature, CCDC 2350516.

Supplementary Data 2

Crystallographic data for compound DFPR2CuBr4 at 240 K, CCDC 2454190.

Supplementary Data 3

Crystallographic data for compound DFPR2CuBr4 at 100 K, CCDC 2428613.

Supplementary Data 4

Crystallographic data for compound DFPP2CuBr4 at room temperature, CCDC 2350517.

Supplementary Data 5

Crystallographic data for compound DFAZ2CuBr4·0.5H2O at room temperature, CCDC 2375732.

Supplementary Data 6

Crystallographic data for compound DFAT2CuBr4 at room temperature, CCDC 2350515.

Supplementary Data 7

Crystallographic data for compound DFPP2CuCl4 at room temperature, CCDC 2428842.

Supplementary Data 8

Crystallographic data for compound (R-3FP)2CuCl4 at room temperature, CCDC 2429039.

Supplementary Data 9

Crystallographic data for compound (R-3FP)2CuCl4 at 340 K, CCDC 2429040.

Source data

Source Data Fig. 3 (download XLSX )

Statistical source data for Fig. 3d,f,g.

Source Data Fig. 4 (download XLSX )

Statistical source data for Fig. 4a–e.

Source Data Fig. 5 (download XLSX )

Statistical source data for Fig. 5c–f,i.

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Wang, M., Yuan, S., Jiang, D. et al. Two-dimensional mixed tetrahedral–octahedral hybrid perovskites with coexisting ferroelectricity and intralayer antiferromagnetism. Nat. Synth 5, 445–454 (2026). https://doi.org/10.1038/s44160-025-00942-0

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