Triangular dodecahedral Dy(III) single-ion magnets with pseudo-mono-axial ligand field

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-09-29 DOI:10.1016/j.molstruc.2025.144203

Yawen Wang , Hong Li , Shaojun Zheng , Lei Chen , Shu-Chang Luo , Peipei Cen , Ulli Englert

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Abstract

Taking advantage of a bulky heptadentate organic ligand tris{[2-((imidazol-4-yl)methyl)amino]ethyl}amine (L) weakly binding to the central Dy(III) ion, two new eight-coordinate triangular dodecahedral Dy(III) complexes, [Dy(L)(F₅PhO)₂](BPh₄)₂·2CH₃CN (F₅PhOH = pentafluorophenol, 1) and [Dy(L)(2,6-dichloro-4-nitro-PhO)](BPh₄)₂·CH₃CN (2,6-dichloro-4-nitro-PhOH = 2,6-dichloro-4-nitrophenol, 2), were synthesized and characterized by X-ray diffraction, magnetic measurements, and theoretical calculations. Complexes 1 and 2 exhibit typical single-molecule magnet (SMM) behavior, with effective energy barriers of 69(6) K and 35(1) K, respectively. Detailed ab initio calculations were performed to further elaborate on the electronic and magnetic structures of the low-lying energy levels for both complexes. The theoretical results indicate that the presence of strongly electron-withdrawing substituents such as fluorine, chlorine, and nitro groups in the axial ligands leads to the reduction of the negative charge distribution in the axial ligand field, thus weakening the magnetic anisotropy of the oblate-shaped Dy(III) ion, which is also confirmed by the analysis of magneto-structural relationship.

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具有伪单轴配体场的三角形十二面体Dy（III）单离子磁体

利用体积较大的七尖酸有机配体三{[2-（咪唑-4-基）甲基)氨基]乙基}胺(L)与中心的Dy（III）离子弱结合，合成了两个新的八坐标三角形十二面体Dy（III）配合物[Dy(L)（F₅PhO）₂](BPh4)2·2CH3CN （F₅PhOH =五氟苯酚，1）和[Dy(L)(2,6-二氯-4-硝基-PhO)](BPh4)2·CH3CN(2,6-二氯-4-硝基-PhOH = 2,6-二氯-4-硝基苯酚，2)，并通过x射线衍射、磁测量、还有理论计算。配合物1和2表现出典型的单分子磁体（SMM）行为，有效能垒分别为69(6)K和35(1)K。进行了详细的从头计算，进一步阐述了这两种配合物的低能级的电子和磁性结构。理论结果表明，轴向配体中氟、氯、硝基等强吸电子取代基的存在导致轴向配体场中负电荷分布的减小，从而减弱了扁圆形Dy（III）离子的磁各向异性，磁结构关系分析也证实了这一点。

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

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