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Modification of magnetocaloric properties upon a change in the spin state of iron(III) in tetrapyrrole paramagnets
Synthetic Metals ( IF 4.0 ) Pub Date : 2021-01-23 , DOI: 10.1016/j.synthmet.2021.116696
Victor V. Korolev , Tatyana N. Lomova , Anna G. Ramazanova , Olga V. Balmasova , Elena G. Mozhzhukhina

Porphyrin complexes of 3d-metals with an open electronic shell are ranked as molecular materials with both electronic functionality and paramagnetic behavior due to exhibiting a positive magnetocaloric effect (MCE) at the temperature close to the room. We have determined MCE, heat, and an enthalpy/entropy change during magnetization of chloride ligated pentacoordinated iron(III) 5,10,15,20-tetraphenylporphin, (Cl)FeTPP and dimethylformamide ligated sixcoordinated iron(III) mesoporphyrin IX, [(DMF)2FeMP]+Cl- at 278–338 K in magnetic fields from 0 to 1.0 T by the direct microcalorimetric method. The specific heat capacity in solid (Cl)FeTPP/[(DMF)2FeMP]+Cl- was directly determined depending on the temperature in zero magnetic fields using DSC. To improve understanding of the correlation between magnetic properties of the iron(III) complexes and its spin state, we have compared the magnetic behavior of paramagnets studied with those for manganese(III) porphyrins. Both the iron(III) spin state and the exchange (ferromagnetic or antiferromagnetic depending on functional substitution in a complex) between a paramagnetic ligand and the central ion are reflected in the magnetocaloric behavior of iron(III) porphyrins studied.



中文翻译:

在四吡咯顺磁体中铁(III)的自旋态改变时磁热性质的改变

的3个卟啉络合物d以开放电子外壳-metals被排名与该两个电子的功能和顺磁性行为由于表现出在该温度接近室温的正的磁热效应(MCE)的分子的材料。我们已经确定了氯化物连接的五配位铁(III)5,10,15,20-四苯基卟啉,(Cl)FeTPP和二甲基甲酰胺连接的六配位铁(III)的中卟啉磁化过程中的MCE,热和焓/熵变化。 DMF)2 FEMP] +-在由直接方法微量在磁场278-338ķ从0至1.0吨。固体(Cl)FeTPP / [(DMF)2 FeMP] + Cl的比热容-使用DSC直接根据零磁场中的温度确定温度。为了更好地理解铁(III)配合物的磁性与其自旋态之间的关系,我们比较了顺磁性和锰卟啉的顺磁性。铁(III)的自旋态和顺磁性配体与中心离子之间的交换(铁磁性或反铁磁性,取决于复合物中的功能取代)取决于所研究的铁(III)卟啉的磁热行为。

更新日期:2021-01-24
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