Syntheses, Structures and Magnetism of Trinuclear Bimetallic MnIILnIIIMnII Complexes (Ln = La, Nd, Sm, Gd, Dy and Er) with 2,6-Dipicolinoylbis(N,N-Diethylthiourea)

IF 2.2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR European Journal of Inorganic Chemistry Pub Date : 2024-08-14 DOI:10.1002/ejic.202400366
Prof. Chien Thang Pham, Dang Hung Pham, Dr. Canh Dinh Le, Dr. Thu Ha Nguyen, Prof. Minh Hai Nguyen, Prof. Kenji Matsumoto, Prof. Hung Huy Nguyen
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Abstract

Self-assembled reactions of 2,6-dipicolinoylbis(N,N-diethylthiourea) (H2L) with Mn(CH3COO)2 ⋅ 4H2O and LnCl3, where Ln = La, Nd, Sm, Gd, Dy, Er in MeOH lead to formation of stable trinuclear complexes of the composition [LnMn2(L)21,3-CH3COO)2X] (MnIILnIIIMnII), where X can be κ2-CH3COO or κ1-CH3COO. Single crystal X-ray studies reveal their symmetric structures comprising one central Ln(III) ion, two terminal Mn(II) ions sandwiched by two doubly deprotonated ligands {L2−}. The magnetic properties of MnIILaIIIMnII and MnIIGdIIIMnII complexes are successfully simulated using symmetrical magnetic interaction models, giving the best fitted parameters: JMn-Mn=−0.120(1) cm−1, gMn=1.99(1), TIP=4.45(7) ⋅ 10−4 cm3 mol−1 K for MnIILaIIIMnII and JGd-Mn=0.042(1) cm−1, JMn-Mn=−0.076(1) cm−1, gMn=1.96(1), gGd=2.01(1) and TIP=3.59(14) ⋅ 10−4 cm3 mol−1 K for MnIIGdIIIMnII complex. The magnetic interactions between the Mn(II) and Ln(III) ions in the other MnIILnIIIMnII complexes are studied by comparing their χM values to the sum of χM values of the MnIILaIIIMnII and the analogous ZnIILnIIIZnII complexes. The MnIIErIIIMnII complex reveals a strong ferromagnetic interaction, while the Sm, Nd, Gd and Dy complexes show weak ferromagnetic interactions.

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2,6-Dipicolinoylbis(N,N-diethylthiourea) 三核双金属 MnIILnIIIMnII 配合物(Ln = La、Nd、Sm、Gd、Dy 和 Er)的合成、结构和磁性
2,6-二二甲酰基双(N,N-二乙基硫脲)(H2L)与 Mn(CH3COO)2 ∙ 4H2O 和 LnCl3(其中 Ln = La、Nd、Sm、Gd、Dy)在 MeOH 中的自组装反应导致形成成分为[LnMn2(L)2(μ1,3-CH3COO)2X](MnIILnIIIM)的稳定三核配合物、Er 在 MeOH 中会形成成分为 [LnMn2(L)2(μ1,3-CH3COO)2X] (MnIILnIIIMnII)的稳定三核配合物,其中 X- 可以是 κ2-CH3COO- 或 κ1-CH3COO-。单晶 X 射线研究揭示了它们的对称结构,包括一个中心 Ln(III)离子、两个末端 Mn(II)离子和两个双去质子化配体 {L2-} 。利用对称磁相互作用模型成功模拟了 MnIILaIIIMnII 和 MnIIGdIIIMnII 复合物的磁性能,并给出了最佳拟合参数:对于 MnIILaIIIMnII 而言,JMn-Mn = -0.120(1) cm-1, gMn = 1.99(1), TIP = 4.45(7)∙10-4 cm3 mol-1 K;对于 MnIGdIIIMnII 而言,JGd-Mn = 0.042(1) cm-1, JMn-Mn = -0.076(1) cm-1, gMn = 1.96(1), gGd = 2.01(1) 和 TIP = 3.59(14)∙10-4 。通过比较其他 MnIILnIIIMnII 复合物的 χM 值与 MnIILaIIIMnII 和类似 ZnIILnIIIZnII 复合物的 χM 值之和,研究了其他 MnIILnIIIMnII 复合物中 Mn(II) 离子和 Ln(III) 离子之间的磁相互作用。MnIIErIIIMnII 复合物显示出强铁磁相互作用,而 Sm、Nd 和 Dy 复合物则显示出弱铁磁相互作用。
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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
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