Citation: Xiao-Qin WEI, Zhuan GAO, Fan REN, Xiao-You CUI, Yue ZHOU, Dong SHAO. A Halogen Hydrogen-Bonded Fe(Ⅲ) Complex Showing Hysteretic Spin-Crossover Behavior above Room Temperature[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(11): 2283-2290. doi: 10.11862/CJIC.2022.235 shu

A Halogen Hydrogen-Bonded Fe(Ⅲ) Complex Showing Hysteretic Spin-Crossover Behavior above Room Temperature

Xiao-Qin WEI ¹ ,
Zhuan GAO ¹ ,
Fan REN ¹ ,
Xiao-You CUI ¹ ,
Yue ZHOU ² ,
Dong SHAO ^{2, 3,,}

1.
Shanxi Province Collaborative Innovation Center for Light Materials Modification and Application, Department of Material Science and Engineering, Jinzhong University, Jinzhong, Shanxi 030619, China
2.
Hubei Key Laboratory of Processing and Application of Catalytic Materials, College of Chemistry and Chemical Engineering, Huanggang Normal University, Huanggang, Hubei 438000, China
3.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210023, China

Corresponding author: Dong SHAO, shaodong@nju.edu.cn
Received Date: 6 April 2022
Revised Date: 19 September 2022

Figures(7)

A mononuclear Fe(Ⅲ) complex, [Fe^Ⅲ(bzimpy-1H)₂]Cl (1) was prepared by the reaction of a tridentate ligand 2, 6-bis(benzimidazol-2-yl)pyridine (bzimpy), where bzimpy-1H is the product of bzimpy after removing one proton, and its structure and magnetic properties were characterized in detail. The single crystal structure analysis shows that the Fe³⁺ center features a rare distorted octahedral N₆ coordination environment for the complex, and the 3D supramolecular structure is constructed by N—H⋯Cl hydrogen bonding between the adjacent cation complex units and counterbalance chloride ions. The complex showed hysteretic spin-crossover (SCO) behavior above room temperature as evidenced by combined magnetic investigations and differential scanning calorimetry measurements (T_1/2↑=345 K, T_1/2 ↓=330 K). In addition, the light-induced excited spin state trapping (LIESST) effect was also observed in the complex. The magnetism-structure relationship shows that the N—H⋯Cl hydrogen bonding plays an important role in the bistable SCO behavior of the complex.
- spin crossover,
- Fe(Ⅲ) complex,
- bistable state,
- hydrogen bond,
- supramolecular interactions
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