Gd-based ferrocene complex with a large magnetocaloric effect from rapid room temperature synthesis

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-08-12 DOI:10.1016/j.jssc.2025.125568

Xiaofei Zhang , Yuwei Wu , Shengqi An , Zhenqian Zhang

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Abstract

We report the fabrication of a novel heterometallic Gd-based ferrocene complex (Gd-Fc MOF) using 1,1′-ferrocenedicarboxylic acid (FDCA) as an organic ligand and gadolinium (III) nitrate hydrate as a metal ion source. Comprehensive investigation of the crystal structure and magnetic properties revealed a remarkable cryogenic magnetocaloric effect (MCE) near the liquefaction temperature of helium T = 2.5 K. Under a magnetic field change of ΔH = 7 T, the maximum entropy change (−ΔS_M^max) reaches to 49.19 J kg⁻¹ K⁻¹. This outstanding MCE arises from the synergistic interplay of the specific assembly structure, properties inherent to the FDCA ligand, and the large spin ground state of Gd³⁺. The Gd-Fc MOF exhibits significant promise for efficient cryogenic magnetic refrigeration in molecular-based systems. This potential arises from its high metal proportion, elevated theoretical magnetic entropy, rapid room-temperature synthesis capability, good magnetocaloric effect (MCE) performance near liquid helium temperatures, and a large calculated relative cooling power (RCP) of 460.7 J kg⁻¹, which demonstrates practical cooling capacity.

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室温快速合成具有大磁热效应的gd基二茂铁配合物

以1,1′-二茂铁羧酸（FDCA）为有机配体，硝酸钆（III）水合物为金属离子源，制备了一种新型异金属gd基二茂铁配合物（Gd-Fc MOF）。晶体结构和磁性能的综合研究表明，在氦液化温度T = 2.5 K附近存在显著的低温磁热效应。当磁场变化ΔH = 7 T时，最大熵变（−ΔSMmax）达到49.19 J kg−1 K−1。这种突出的MCE源于特定组装结构、FDCA配体固有特性和Gd3+的大自旋基态的协同相互作用。Gd-Fc MOF在分子基系统中显示出高效低温磁制冷的重要前景。该材料具有较高的金属比例、较高的理论磁熵、快速的室温合成能力、在液氦温度附近良好的磁热效应（MCE）性能以及高达460.7 J kg−1的计算相对冷却功率（RCP），证明了其实际冷却能力。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.