Citation: Junyang FENG, Xiaoli HAN, Yongjie SONG, Gang LI. Proton conduction and fluorescence properties of an ionic hydrogen-bonded organic framework constructed from dibromophthalic acid[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(4): 693-702. doi: 10.11862/CJIC.20250350 shu

Proton conduction and fluorescence properties of an ionic hydrogen-bonded organic framework constructed from dibromophthalic acid

1.
College of Modern Biology and Pharmacy, Henan Technical Institute, Zhengzhou 450042, China
2.
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China

Corresponding author: Gang LI, gangli@zzu.edu.cn
Received Date: 24 November 2025
Revised Date: 6 January 2026

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To address the pressing demand for proton-conducting materials with enhanced environmental adaptability and long-term stability, an ionic hydrogen-bonded organic framework (iHOF 1) was successfully constructed via a solvothermal method using 2, 5-dibromoterephthalic acid (H₂BDC-Br₂) as the building block. Its crystal structure, stability profiles, proton transport behavior, and photoluminescent properties were systematically investigated by a combination of characterization techniques, including single-crystal X-ray diffraction, powder X-ray diffraction, electrochemical impedance spectroscopy, solid-state fluorescence spectroscopy, etc. Structural analysis reveals that iHOF 1 crystallizes in the monoclinic space group C2/c, with its 3D framework stabilized by robust intermolecular H-bonds and electrostatic interactions between HBDC-Br₂^- anions and (Me₂NH₂)⁺ cations. Proton conductivity measurements demonstrate a distinct dependence on both temperature and relative humidity (RH), reaching a maximum value of 1.72×10^-3 S·cm^-1 at 100 ℃ and 98% of RH. Activation energy calculations yield values of 0.44 eV (at 68% of RH) and 0.41 eV (at 98% of RH), confirming that proton transport within the framework follows the Grotthuss hopping mechanism. This efficient proton conduction is facilitated by a contiguous H-bonded network formed by hydrophilic carboxyl groups, bromine atoms, and (Me₂NH₂)⁺ cations in the framework. Stability assessments indicated that iHOF 1 possessed excellent thermal stability (decomposition temperature: 230 ℃) and chemical stability, as evidenced by the retention of structural integrity after water immersion and prolonged electrochemical testing. Furthermore, upon excitation at 324 nm, the material exhibited a strong and monochromatic blue emission peak at 432 nm, which originates from the π→π* transition of the aromatic moieties and is significantly enhanced by the confinement effect of the rigid framework.
- 2，5-dibromoterephthalic acid,
- hydrogen-bonded organic framework,
- crystal structure,
- proton conduction,
- solid-state fluorescence
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1.
沈阳化工大学材料科学与工程学院沈阳 110142