Inducing Ferrimagnetic Exchange in 1D-FeSe2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe2]2,Inorganic Chemistry

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Inducing Ferrimagnetic Exchange in 1D-FeSe2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe2]2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-01-22 , DOI: 10.1021/acs.inorgchem.3c03440
Eranga H Gamage _{1,

2} , Saeed Kamali _{3,

4} , Govind Sasi Kumar ₅ , Judith K Clark ₅ , Yongbin Lee ₂ , Yao Abusa ₁ , Philip Yox _{1,

2} , Liqin Ke ₂ , Michael Shatruk _{5,

6} , Kirill Kovnir _{1,

2}

Affiliation

[Fe(en)(tren)][FeSe₂]₂ (en = ethylenediamine, C₂H₈N₂, tren = tris(2-aminoethyl)amine, C₆H₁₈N₄) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)]²⁺ complexes with distorted octahedral coordination, incorporated between 1D-FeSe₂ chains composed of edge–sharing FeSe₄ tetrahedra. The twisted octahedral coordination environment of the Fe–amine complex leads to partial dimerization of Fe–Fe distances in the FeSe₂ chains so that the FeSe₄ polyhedra deviate strongly from the regular tetrahedral geometry. ⁵⁷Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fe^chain atoms and +2 for the Fe^complex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie–Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe₂ chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe–Se fragments. This synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe–Se chains.

中文翻译：

使用杂配胺络合物诱导 1D-FeSe2 链中的亚铁磁交换：[Fe(en)(tren)][FeSe2]2

[Fe(en)(tren)][FeSe ₂ ] ₂ ( en = 乙二胺，C ₂ H ₈ N ₂ ， tren = 三(2-氨基乙基)胺，C ₆ H ₁₈ N ₄ ) 已通过混合合成配体溶剂热法。其晶体结构包含具有扭曲八面体配位的杂配[Fe(en)(tren)] ²⁺配合物，结合在由共享边缘的FeSe ₄四面体组成的1D-FeSe ₂链之间。 Fe-胺配合物的扭曲八面体配位环境导致FeSe ₂链中Fe-Fe距离的部分二聚化，使得FeSe ₄多面体强烈偏离规则四面体几何形状。 ⁵⁷ Fe 穆斯堡尔光谱显示 Fe^链原子的氧化态为 +3，Fe^络合物原子的氧化态为 +2。链中 Fe 原子的紧密接近促进了铁磁最近邻相互作用，如正 Weiss 常数 θ = +53.8(6) K（源自居里-Weiss 拟合）所示。磁力测量和热容量揭示了低于 10 K 的两个连续磁转变。DFT 计算表明，在 4 K 处观察到的有序性是由于 1D-FeSe ₂链中的反铁磁链内相互作用所致。两种不同配体的组合产生了不对称的配位环境，从而引起 Fe-Se 片段结构的变化。这种合成策略开辟了探索配体场强对 Fe-胺配合物和周围 Fe-Se 链结构影响的新方法。

更新日期：2024-01-22

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