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

doi:10.6023/A23030064

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

Article

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^,^*()

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

Jian Chen^a, Zhuoer Cai^a, Shulin Jiao^a, Xiang Zhang^a, Jinzhong Hu^a, Min Liu^a, Baiwang Sun^a(), Xiuni Hua^b()

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: chmsunbw@seu.edu.cn; huaxiuni@njxzc.edu.cn
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)

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Abstract

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 E_g 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

Cite this article

Jian Chen, Zhuoer Cai, Shulin Jiao, Xiang Zhang, Jinzhong Hu, Min Liu, Baiwang Sun, Xiuni Hua. A Thermally Responsive Dielectric Switchable Zero-Dimensional Organic-Inorganic Hybrid Material: (C₃H₆NH₂)₂CoCl₄[J]. Acta Chimica Sinica, 2023, 81(5): 480-485.

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Fig. & Tab. 8

Figure 1. DSC curves of (C3H6NH2)2CoCl4

Figure 2. 293 K, (a) structural unit and (b) crystal stacking diagram of (C3H6NH2)2CoCl4 (green dashed lines are hydrogen bonds, ellipsoidal rates are set at the 10% probability level)

Figure 3. 353 K, (a) structural unit and (b) crystal stacking diagram of (C3H6NH2)2CoCl4 (green dashed lines are hydrogen bonds, ellipsoidal rates are set at the 10% probability level)

Figure 4. Variation of the real part of the dielectric constant (ε') of (C3H6NH2)2CoCl4 with temperature at different frequencies, where HTP and LTP refer to the high-temperature and low-temperature phases respectively

Figure 5. Temperature variation curve for (C3H6NH2)2CoCl4 values of ε' at 1 MHz

Figure 6. Dielectric switching cycle testing of (C3H6NH2)2CoCl4 at 1 MHz

Figure 7. 3D Hirshfeld surface and 2D finger plots of (C3H6NH2)2CoCl4 in the low temperature phase (293 K)

Figure 8. UV-Vis absorption spectra of (C3H6NH2)2CoCl4

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

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

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