Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (5): 480-485.DOI: 10.6023/A23030064 Previous Articles     Next Articles


一种热响应介电开关型零维有机-无机杂化材料: (C3H6NH2)2CoCl4

陈剑a, 蔡卓尔a, 焦淑琳a, 张祥a, 胡进忠a, 刘敏a, 孙伯旺a,*(), 花秀妮b,*()   

  1. a 东南大学 化学化工学院 南京 211189
    b 南京晓庄学院 环境科学学院 南京 211171
  • 投稿日期:2023-03-04 发布日期:2023-04-27
  • 作者简介:
    † 共同第一作者
  • 基金资助:
    受国家自然科学基金(22201134); 江苏省高校自然科学基金(22KJB150028)

A Thermally Responsive Dielectric Switchable Zero-Dimensional Organic-Inorganic Hybrid Material: (C3H6NH2)2CoCl4

Chen Jiana, Cai Zhuoera, Jiao Shulina, Zhang Xianga, Hu Jinzhonga, Liu Mina, Sun Baiwanga(), Hua Xiunib()   

  1. a School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189
    b School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171
  • Received:2023-03-04 Published:2023-04-27
  • Contact: *E-mail:;
  • About author:
    † These authors contributed equally to this work
  • Supported by:
    National Natural Science Foundation of China(22201134); Natural Science Foundation for Colleges and Universities of Jiangsu Province(22KJB150028)

Stimuli-responsive smart materials have garnered significant interest due to their potential applications in information storage and sensors. These materials possess a simple preparation process, versatile structure, and are cost-effective, particularly the organic-inorganic hybrid-type thermally responsive dielectric switching materials. To this end, we selected azetidine hydrochloride and cobalt chloride hexahydrate and utilized a straightforward solvent evaporation method to obtain blue transparent crystals, (C3H6NH2)2CoCl4, a zero-dimensional organic-inorganic hybrid material exhibiting temperature responsiveness. It is notable that this compound undergoes a reversible structural phase transition at 347.7 K. And the enthalpy change of the material was consistent, as revealed by the differential scanning calorimetry (DSC) curves tested at different ramp-up and ramp-down rates. The heat absorption and exothermic peaks also displayed consistency at different rates, with the peaks demonstrating a tendency to contract. The crystal structure of the material underwent a phase transition from P21/n to Pnma space group, as evidenced by single crystal X-ray diffraction (SCXRD) data at variable temperatures. This transition was attributed to the deformation and displacement of the (CoCl4)2- anions and the ordered-disordered movements of the (C3H6NH2)+ cation. The dielectric test results of (C3H6NH2)2CoCl4 exhibited a step-like dielectric anomaly, with consistent dielectric changes over several dielectric cycles, demonstrating excellent dielectric switching properties. Weak interactions around the cations were calculated by Crystal Explorer, indicating that the main cause of the hybrid material formation was due to H•••H interactions between the cations and H•••Cl interactions between the anions and cations. Additionally, based on the ultraviolet-visible absorption spectroscopy, (C3H6NH2)2CoCl4 displayed an absorption edge at 743 nm, with an estimated optical bandgap Eg of 4 eV. Moreover, the material demonstrated exceptional stability, cycle life, and durability, indicating its potential for a wide range of applications in energy storage, sensors, catalysts, and other fields. In conclusion, this work provides novel insights into the structural design and property modulation of organic-inorganic hybrid materials.

Key words: organic-inorganic hybrid, structural phase transition, ordered-disordered movements, thermal response, dielectric switch