酸性离子液调控下咪唑硫酸四铁簇合物和铁-DMSO配合物的合成（英文）

Syntheses of Imidazole Template Fe_4 Sulfate Clusters and Iron-DMSO Complex Mediated by Br?nsted Acid Ionic Liquids

FeCl_2与酸性离子液在乙醇中反应制备得到咪唑硫酸铁簇合物[HMIM]_2[Fe_2O(SO_4)_3(DMSO)_2]·0.5DMSO(1)和[HPIM]_4[Fe_4O_2(SO_4)_6(DMSO)_4]·2MeCN(2),该类簇合物为四核铁簇Fe_4(O)_2(SO_4)_6(DMSO)_4结构,4个Fe原子通过中心μ3-O桥、硫酸根上的μ2-O和μ3-O桥连接,形成共平面结构,中间的四核铁簇为-4价,4个质子化的咪唑正离子起电荷平衡作用。该簇合物的晶体结构属于三斜晶系中的P1空间群。变温磁化率测试表明该簇合物具有强的反铁磁性。但在类似的反应条件下,FeCl_3在酸性离子液反应没有得到类似的簇合物,而是得到DMSO配合物[FeCl_2(DMSO)_4][EtSO_4]·DMSO(3)。

Imidazole template iron sulfate clusters,[HMIM]2[Fe2O（SO4）3（DMSO）2]·0.5DMSO （1） and[HPIM]4[Fe4O2（SO4）6（DMSO）4]·2MeCN （2）, were synthesized via the reaction of FeCl2 with Br？nsted acidic ionic liquid[HRIM] [HSO4] using ethanol as solvent. The clusters crystallize in triclinic with a space group P1. The core contains 4 iron atoms, which are coplanar connected by the central μ3-O bridge, μ2-O and μ3-O bridge of SO4 groups. Protonated imidazoliums are the counter cations for the balance of charges of the core. Variable temperature magnetic susceptibility measurements of the Fe4 sulfate clusters reveal weak antiferromagnetic exchange interactions between the metal centers. In contrast, the reaction of FeCl3 under the similar experimental conditions didn＇t produce the similar cluster structure, whereas iron-DMSO complex[FeCl2（DMSO）4] [EtSO4]·DMSO （3） was obtained.