Halogen-Driven Spin Dynamics: Exploring Correlation of Cooperativity and Spin Crossover in Solid-State Mononuclear Fe(III) Schiff-Base Complexes

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-03-27 DOI:10.1021/acs.inorgchem.5c00885

Li-Wen Chen, Hai Zhu, Hua-Wei Zhou, Hao-Zhe Zhang, Sheng-Ze Zhao, Yong-Hua Li, Shi Wang

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Abstract

We report the synthesis, crystal structures, and magnetic properties of four new mononuclear iron(III) complexes, [Fe(5-X-sal₂trien)]ReO₄ (X = F (1); X= Cl (2); X = Br (3); X = I (4)), where (5-X-sal₂trien)^2– is a halogen-substituted hexadentate Schiff-base (N₄O₂)^2– ligand. Magnetic susceptibility measurements demonstrated that complex 1 maintains a high-spin (HS) state, while complexes 3 and 4 display a very gradual spin crossover (SCO) above 300 K. Complex 2 exhibits a unique two-step thermo-induced spin-state switching at T_1/2 = 250 K (1) and 209 K (2) with symmetry breakings. Single-crystal X-ray structures of 2 are obtained at 300, 250, and 100 K, respectively, indicating two structural phase transitions (Pccn–Pmmn–P2₁/m). The introduction of halogen substituents on (sal₂trien)^2– ligands has a great influence on cooperativity and finally the magnetic properties of Fe(III) SCO complexes.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.