Proton Alloying in an Organic‐Inorganic Hybrid Material Enables Unusual Dynamic Birefringence and Martensitic Actuation

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 Lei Pan (Department of Chemistry) C Cha‐Hui Du (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 Le‐Chu Xu (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) J Jun‐Chao Lou (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) P Pei‐Guo Liu (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) H Hui‐Nan Wang (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 Chang‐Feng Wang (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) 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) Y Yi Zhang

Abstract

Abstract Alloying is widely recognized as an effective strategy for enhancing or unlocking material properties by combining different elements. Organic‐inorganic hybrid materials (OIHMs) allow for chemical modification at the molecular level, bringing new opportunities and enormous potential to alloying strategies. Hydrogen protons in molecules are essential for structural design and crystal engineering, however, valuable role of proton alloying in OIHMs remains largely unexplored. Herein, for the first time, we present a proton alloying OIHM [Cyclen 4+ Cyclen 2+ ]Sb 2 Cl 12 (Cyclen‐1D), which exhibits exceptional martensitic actuation behaviors, including jumping, bending and a significant raising effect with a large expansion up to 50%. Meanwhile, Cyclen‐1D also possesses unusual multi‐mode dynamic birefringence featuring continuous modulation and switching mutation, showing an excellent birefringence change ( Δn  ≈ 0.044). This interesting integration of mechanical and optical channels originates from the asynchronous orientations of distinct protonated Cyclen cations as well as cooperative transformation with inorganic octahedron through hydrogen bonding. This work reveals the great potential of proton alloying in OIHMs, opening new avenues for designing dynamically stimuli‐responsive materials.

Article Details

Volume / Issue Vol. 64, Issue 51
Published December 15, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (11)

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

Lei Pan

Department of Chemistry

C

Cha‐Hui Du

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

Le‐Chu Xu

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

J

Jun‐Chao Lou

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

P

Pei‐Guo Liu

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

H

Hui‐Nan Wang

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

Chang‐Feng Wang

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

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

Y

Yi Zhang