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含两个吡啶侧臂的吡啶基大环配体钴（II）配合物的合成、结构及磁性性质

Synthesis, structural and magnetic properties of cobalt(ii) complexes with pyridine-based macrocyclic ligand containing two pyridine pendant arms.

作者信息

Zahradníková Eva, Pichon Céline, Duhayon Carine, Sutter Jean-Pascal, Halaš Petr, Drahoš Bohuslav

机构信息

Department of Inorganic Chemistry, Faculty of Science, Palacký University Olomouc 17. listopadu 12 CZ-771 46 Olomouc Czech Republic

Laboratoire de Chimie de Coordination du CNRS (LCC-CNRS), Université de Toulouse, CNRS Toulouse France

出版信息

RSC Adv. 2024 Sep 3;14(38):28138-28147. doi: 10.1039/d4ra02387k. eCollection 2024 Aug 29.

DOI:10.1039/d4ra02387k
PMID:39228762
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11369886/
Abstract

With the aim of tuning the magnetic anisotropy, a series of Co(ii) complexes with the general formula of complex cations [Co(L)X], where X = Br (1); I (2); NCO (3); NCS (4a); N (5), and [Co(L)(NCS)] (4b), (L = a 17-membered pyridine-based NO-macrocyclic ligand containing two pyridin-2-ylmethyl pendant arms) were prepared and thoroughly characterized. The molecular structures for all complexes showed strongly distorted geometry in between octahedral and trigonal prismatic. The magnetic studies confirmed substantial magnetic anisotropy with positive values of , the axial zero-field splitting parameter, but / ratios close to 1/3. This was supported by theoretical CASSCF calculations showing no significant effect of the co-ligands. Complex 4b was found to behave as a field-induced SMM.

摘要

为了调节磁各向异性，制备了一系列通式为配合物阳离子[Co(L)X]的钴(II)配合物，其中X = Br (1)；I (2)；NCO (3)；NCS (4a)；N (5)，以及[Co(L)(NCS)] (4b)，(L = 一种含两个吡啶-2-基甲基侧臂的17元吡啶基NO大环配体)，并对其进行了全面表征。所有配合物的分子结构在八面体和三角棱柱之间呈现出强烈扭曲的几何形状。磁性研究证实了具有显著的磁各向异性，轴向零场分裂参数为正值，但/比值接近1/3。这得到了理论CASSCF计算的支持，该计算表明共配体没有显著影响。发现配合物4b表现为场诱导单分子磁体。

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