Citation: Guang-Yan Xu, Shuang Peng, Zi-Han Yan, Ying-Ying Wu, Feng-Lei Yang, Jing-Wei Dai, Zhao-Yang Li. Precise control of the spin-crossover transition temperature in Fe(Ⅲ)/Cr(Ⅲ) molecular solid solutions[J]. Chinese Chemical Letters, ;2026, 37(12): 111898. doi: 10.1016/j.cclet.2025.111898 shu

Precise control of the spin-crossover transition temperature in Fe(Ⅲ)/Cr(Ⅲ) molecular solid solutions

Guang-Yan Xu ^a ,
Shuang Peng ^b ,
Zi-Han Yan ^a ,
Ying-Ying Wu ^a ,
Feng-Lei Yang ^{c, *,} ,
Jing-Wei Dai ^d ,
Zhao-Yang Li ^{a, *,}

a.
School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
b.
College of Chemistry, Nankai University, Tianjin 300071, China
c.
Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, School of Chemistry and Material Science, Jiangsu Normal University, Xuzhou 221116, China
d.
State Key Laboratory of Medicinal Chemical Biology, Nankai University, Tianjin 300071, China

yangfl@jsnu.edu.cn

zhaoyang@nankai.edu.cn

Received Date: 18 August 2025
Revised Date: 10 September 2025
Accepted Date: 24 September 2025
Available Online: 25 September 2025

Figures(5)

Spin-crossover (SCO) materials exhibit reversible transitions between high-spin (HS) and low-spin (LS) states and are potentially multifunctional; however their practical deployment is hindered by limited operating-temperature windows. While metal-ion dilution using molecular solid solutions has emerged as a powerful strategy for modulating Fe(Ⅱ) SCO systems, analogous approaches for Fe(Ⅲ) systems remain unexplored. Herein, we report the first successful incorporation of paramagnetic Cr(Ⅲ) into the [Fe^Ⅲ(HL^Cl)(L^Cl)]·H₂O Fe(Ⅲ) SCO complex and the construction of isostructural {[Fe^Ⅲ(HL^Cl)(L^Cl)]_1-_x[Cr^Ⅲ(HL^Cl)(L^Cl)]_x}·H₂O (x = 0.1–0.9) molecular solid solutions. Variable-temperature magnetic susceptibility and differential scanning calorimetry (DSC) studies revealed that increasing the Cr(Ⅲ) concentration led to a systematic reduction in spin-transition temperature (T_c). Single-crystal X-ray diffractometry confirmed that the monoclinic P2₁/n symmetry is conserved across the solid-solution series, while structural analysis revealed Cr-induced octahedral distortion at the metal centers. Density functional theory (DFT) calculations establish that Cr(Ⅲ) doping stabilizes the HS state and diminishes Fe···Fe cooperativity through site-specific perturbations, resulting in lower T_c values and slower spin-transition kinetics. This study provides a novel pathway for precise T_c engineering in Fe(Ⅲ) SCO systems, thereby significantly advancing their use in data-storage and sensing-technology applications.
- Spin crossover,
- Metal-ion dilution,
- Molecular solid solution,
- Fine-tuning the spin transition temperature,
- Magnetic property
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