Alkaline Earth Metal‐Based Hybrid Organic‐Inorganic Perovskite‐Like Ferroelectrics

Q Qi‐Fang Zhou (Institute for Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P.R. China) L Lei Pan (Department of Chemistry) H Hao‐Fei Ni (Institute for Science and Applications of Molecular Ferroelectrics Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P. R. China) L Lou‐Kai Ye (Institute For Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 People's Republic of China) Y Yan‐Ping Zhao (Institute for Science and Applications of Molecular Ferroelectrics Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P.R. China) Q Qing‐Ke Luo (Institute for Science and Applications of Molecular Ferroelectrics Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P.R. China) G Gele Teri J Jia‐Qi Luo (Institute For Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 People's Republic of China) D Da‐Wei Fu (Institute for Science and Applications of Molecular Ferroelectrics Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P. R. China) Z Zhi‐Xu Zhang (Institute for Science and Applications of Molecular Ferroelectrics Key Laboratory of the Ministry of Education for Advanced Catalysis Materials Zhejiang Normal University Jinhua 321004 P. R. China) C Chao Shi Y Yi Zhang

Abstract

AbstractHybrid organic‐inorganic perovskites (HOIPs) with the ABX3 formula have garnered significant scientific interest owing to their substantial technological promise in photovoltaics, optoelectronics and ferroelectrics. Their structural diversity and molecular‐scale chemical programmability provide an exceptional platform for engineering diverse functional HOIP architectures through targeted compositional design. However, the strategic potential of alkaline earth metals (e.g., Ca, Sr, and Ba) in HOIP assembly remains largely unexplored, with ferroelectric implementations yet to be realized, despite their historical roots in perovskite evolution dating back to the eponymous CaTiO3 mineral discovered in 1839. Here, for the first time, we report a new family of alkaline earth metal‐based HOIP‐like ferroelectrics. Benefiting from three‐dimensional cage‐like structure and multiaxial characteristics, (pyrrolidinium)Ba(ClO4)3 as a representative shows pronounced ferroelectricity with robust polarization switching in both bulk single crystals and compressed polycrystalline powder pellets. Molecular fluorination strategy on pyrrolidinium cation further optimizes the comprehensive ferroelectric properties (R‐3‐fluoropyrrolidinium)Ba(ClO4)3, enhancing Curie temperature, increasing polar axes and doubling polarization values. Combined with their easy preparation and good plasticity, this discovery provides a brand‐new structural paradigm for HOIP ferroelectrics and highlights exceptional promise in emerging flexible ferroelectric applications.

Article Details

Volume / Issue Vol. 64, Issue 40
Published September 26, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (12)

Q

Qi‐Fang Zhou

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

L

Lei Pan

Department of Chemistry

H

Hao‐Fei Ni

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

L

Lou‐Kai Ye

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

Y

Yan‐Ping Zhao

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

Q

Qing‐Ke Luo

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

G

Gele Teri

J

Jia‐Qi Luo

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

D

Da‐Wei Fu

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

Z

Zhi‐Xu Zhang

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

C

Chao Shi

Y

Yi Zhang