Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes
Magnetic Interactions in a Series of Homodinuclear Lanthanide Complexes
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DOI：
10.1021/acs.inorgchem.5b01673
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发表时间：
2015-12-07
影响因子：
4.6
通讯作者：
Wadepohl, Hubert
中科院分区：
文献类型：
--
作者：
Comba, Peter;Grosshauser, Michael;Wadepohl, Hubert
本文报道了七个同结构同双核镧系配合物。的磁性（交流和直流SQUID测量）的基础上进行了讨论的X-射线结构特性，这表明两个镧系元素的网站是结构不同的。镝（III）和钕（III）配合物（[Dy-2（III）（L）（OAc）（4）]（+）和[NdIII 2（L）（OAc）（4）]（+））的MCD光谱使我们能够彻底分析配体场，钆（III）物质（[Gd-2（III）（L）（OAc）（4）]（+）的高频EPR光谱显示了偶极耦合在这些系统中的重要性。镝（III）络合物的广泛量子化学分析（[DyIII 2（L）（OAc）4]（+）），涉及从头算（CASSCF）波函数，显式自旋轨道耦合（RASSI-SO）和配体场分析（Lines模型和Stevens算子），与所有实验数据完全一致（SQUID，HF-EPR，MCD），并特别允许我们准确地模拟实验chi T与T数据，因此允许我们建立所有弛豫途径的定性模型。
A series of seven isostructural homodinuclear lanthanide complexes are reported. The magnetic properties (ac and dc SQUID measurements) are discussed on the basis of the X-ray structural properties which show that the two lanthanide sites are structurally different. MCD spectroscopy of the dysprosium(III) and neodymium(III) complexes ([Dy-2(III)(L)(OAc)(4)](+) and [NdIII2(L)(OAc)(4)](+)) allowed us to thoroughly analyze the ligand field, and high-frequency EPR spectroscopy of the gadolinium(III) species ([Gd-2(III)(L)(OAc)(4)](+)) showed the importance of dipolar coupling in these systems. An extensive quantum-chemical analysis of the dysprosium(III) complex ([DyIII2(L)(OAc)4](+)), involving an ab initio (CASSCF) wave function, explicit spinorbit coupling (RASSI-SO), and a ligand field analysis (Lines model and Stevens operators), is in full agreement with all experimental data (SQUID, HF-EPR, MCD) and specifically allowed us to accurately simulate the experimental chi T versus T data, which therefore allowed us to establish a qualitative model for all relaxation pathways.