SMM behaviour in a {CoIII4CoII2DyIII2} complex: Co(II)-based thermal barrier and Dy(III) spectator role

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-25 DOI:10.1039/d5dt01689d

Lara Martinez, David Hunger, Carlos Cruz, Joris van Slageren, Verónica Paredes-García, Pablo Alborés

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Abstract

We report the synthesis, structure, and magnetic properties of a novel Co/Dy heterometallic complex, [Co^III₄Co^II₂Dy^III₂(tea)₄(CH₃COO)₄(OH)₂(NO₃)₄]·2H₂O (1), the first structurally characterized example of a mixed-valent {Co^III₄Co^II₂Dy^III₂} motif. It comprises two butterfly-like {Co^III₂Co^IIDy^III} units linked by carboxylate and alkoxide bridges. X-ray diffraction shows unique Dy(III) and Co(II) sites, with Dy(III) nine-coordinated and Co(II) in a rhombic tetrahedral geometry. Magnetic data and quantum chemical calculations reveal weak Co(II)–Co(II) antiferromagnetic exchange, negligible Co(II)–Dy(III) interactions, and moderate Co(II) zero-field splitting (D ≈ 12–20 cm⁻¹), which drives single-molecule magnet behavior below 14 K. AC studies indicate multiple tunneling pathways and an Orbach barrier (U_eff ≈ 65 cm⁻¹) arising from Co(II), while Dy(III) ions remain largely magnetically decoupled.

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{CoIII4CoII2DyIII2}配合物中的SMM行为：Co（II）基热障和Dy（III）的旁观作用

我们报道了一种新型Co/Dy异质金属配合物[CoIII4CoII2DyIII2(tea)4(CH3COO)4(OH)2(NO3)4]·2H2O(1)的合成、结构和磁性能，这是混合价{CoIII4CoII2DyIII2}基序的第一个结构表征例子。它包括两个蝴蝶状的{CoIII2CoIIDyIII}单元，由羧酸盐和醇盐桥连接。x射线衍射显示出独特的Dy（III）和Co（II）位点，Dy（III）和Co（II）呈九配位结构，呈菱形四面体结构。磁性数据和量子化学计算表明，弱Co(II) -Co （II）反铁磁交换，可忽略的Co(II) -Dy （III）相互作用，以及适度的Co（II）零场分裂（D≈12-20 cm−1），驱动14 K以下的单分子磁体行为。交流研究表明，Co（II）离子产生了多个隧道通路和奥尔巴赫势垒（Ueff≈65 cm−1），而Dy（III）离子在很大程度上保持了磁去耦。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.