A {Cr4Ln2} Complex with Exchange Coupled {Cr2} Units: Structural Description and Magnetic Study

IF 3.9 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Daiana Cabrosi, Juan H. Mecchia Ortiz, Carlos Cruz, Verónica Paredes-García, Pablo Alborés
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Abstract

We have prepared and structurally characterized pivalate based {CrIII4LnIII2} complexes with Ln = Dy and Gd as well as the Y analogue, with the overall formula [CrIII4LnIII2(mdea)2(piv)10(OH)4], Ln = Gd, Dy and Y. We are reporting a detailed experimental magnetic properties study, including magnetization relaxation dynamics and calorimetric data, supported with quantum chemical calculations. The synthesis of the Y derivative, allowed to precisely identify the Cr(III)-Cr(III) exchange interaction magnitude which proved moderately strong and in agreement with known magneto-structural correlations. This result agrees with the observed double bridged {Cr2-μOH-μOR} units within the {Cr4Ln2} complexes. The Gd(III) complex magnetic properties can be properly described with the already established exchange coupled {Cr2} units, and a unique Gd(III)-Cr(III) exchange coupling parameter which proved anti-ferromagnetic in nature. The MCE characterization of this complex based on magnetization and calorimetric data down to 2 K affords a moderate entropy change value, mainly affected by the strong Cr-Cr exchange interaction. The complex with Ln = Dy, showed SMM behaviour below 10 K under 0 DC applied field with negligible field dependence up to 3000 Oe and 10 kHz of AC field frequency. Two relaxation processes are clearly distinguished, with thermal barriers for an Orbach mechanism of ca. 20 cm−1 and 40 cm−1.

Abstract Image

{Cr4Ln2}交换偶联{Cr2}配合物的结构描述和磁性研究
我们制备并结构表征了Ln=Dy和Gd以及Y类似物的私人酸盐基{CrIII4LnIII2}配合物,其总体公式为[CrIII4LnIII2(mdea)2(piv)10(OH)4], Ln= Gd, Dy和Y。我们报告了详细的实验磁性研究,包括磁化弛豫动力学和量热数据,并支持量子化学计算。Y导数的合成,可以精确地确定Cr(III)-Cr(III)交换相互作用的强度,证明了中等强度,并与已知的磁结构相关性一致。这一结果与在{Cr4Ln2}配合物中观察到的双桥{Cr2-mOH-mOR}单元一致。Gd(III)配合物的磁性可以用已经建立的交换耦合{Cr2}单元和一个独特的Gd(III)-Cr(III)交换耦合参数来描述,该参数被证明是反铁磁性的。基于磁化和量热数据的MCE表征表明,该配合物的熵变值适中,主要受强Cr-Cr交换相互作用的影响。Ln=Dy的配合物在0直流电场下,在10 K以下表现出SMM行为,在3000 Oe和10 kHz交流场频下,场依赖性可以忽略不计。两种弛豫过程被清楚地区分开来,奥尔巴赫机制的热障约为20 cm-1和40 cm-1。
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来源期刊
Chemistry - A European Journal
Chemistry - A European Journal 化学-化学综合
CiteScore
7.90
自引率
4.70%
发文量
1808
审稿时长
1.8 months
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields. Based in Europe Chemistry—A European Journal provides an excellent platform for increasing the visibility of European chemistry as well as for featuring the best research from authors from around the world. All manuscripts are peer-reviewed, and electronic processing ensures accurate reproduction of text and data, plus short publication times. The Concepts section provides nonspecialist readers with a useful conceptual guide to unfamiliar areas and experts with new angles on familiar problems. Chemistry—A European Journal is published on behalf of ChemPubSoc Europe, a group of 16 national chemical societies from within Europe, and supported by the Asian Chemical Editorial Societies. The ChemPubSoc Europe family comprises: Angewandte Chemie, Chemistry—A European Journal, European Journal of Organic Chemistry, European Journal of Inorganic Chemistry, ChemPhysChem, ChemBioChem, ChemMedChem, ChemCatChem, ChemSusChem, ChemPlusChem, ChemElectroChem, and ChemistryOpen.
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