Nature of the Interaction between Ln(III) and Cu(II) Ions in the Ladder-Type Compounds {Ln(2)[Cu(opba)](3)}.S (Ln = Lanthanide Element; opba = ortho-Phenylenebis(oxamato), S = Solvent Molecules).
Nature of the Interaction between Ln(III) and Cu(II) Ions in the Ladder-Type Compounds {Ln(2)[Cu(opba)](3)}.S (Ln = Lanthanide Element; opba = ortho-Phenylenebis(oxamato), S = Solvent Molecules).
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DOI：
10.1021/ic9811998
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发表时间：
1999-08
影响因子：
4.6
通讯作者：
M. Kahn;C. Mathonière;O. Kahn
中科院分区：
文献类型：
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作者：
M. Kahn;C. Mathonière;O. Kahn
迄今为止，大多数涉及 4f-3d 化合物磁性的研究仅限于 4f 离子为具有纯自旋基态的 Gd(III) 的情况。对于具有一级轨道动量的镧系(III)离子，确定4f-3d相互作用的性质仍然是一个挑战。本文解决了这个问题。研究了式{Ln(2)[M(opba)](3)}.S(以下简称Ln(2)M(3))化合物的磁性能； Ln代表镧系元素，M代表Cu或Zn，opba代表邻亚苯基双(oxamato)，S代表溶剂分子。所有这些化合物都具有相似的由梯型基序组成的一维结构。我们的方法包括比较每个 Ln(III) 离子的 Ln(2)Cu(3) 和 Ln(2)Zn(3) 的磁性。前者受 Ln(III) 斯塔克组分的热布居和 Ln(III)-Cu(II) 相互作用控制；后者仅受 Ln(III) Stark 组分的热布居控制。已证实Gd(III)-Cu(II)相互作用是铁磁性的，并且发现Tb(III)-Cu(II)和Dy(III)-Cu(II)相互作用也是铁磁性的。 Tm(III)-Cu(II) 相互作用也可能是铁磁性的；然而，情况并不确定。另一方面，在所有其他情况下，Ln(III)-Cu(II) 相互作用都不是铁磁性的；它要么无法通过磁性技术检测，要么通过反铁磁性技术检测到。 Dy(III)-Cu(II)（铁磁性）和 Ho(III)-Cu(II)（非铁磁性）之间的差异尤其显着。对这些发现进行了讨论。
To date, most of the studies dealing with the magnetic properties of 4f-3d compounds have been limited to the case in which the 4f ion was Gd(III), with a pure spin ground state. For the lanthanide(III) ions with a first-order orbital momentum, the determination of the nature of the 4f-3d interaction is still a challenge. This paper addresses this problem. The magnetic properties of the compounds of formula {Ln(2)[M(opba)](3)}.S (abbreviated hereafter as Ln(2)M(3)) have been investigated; Ln stands for a lanthanide element, M for Cu or Zn, opba for ortho-phenylenebis(oxamato), and S for solvent molecules. All of these compounds have similar one-dimensional structures consisting of ladder-type motifs. Our approach consisted of comparing the magnetic properties of Ln(2)Cu(3) and Ln(2)Zn(3) for each Ln(III) ion. The former are governed by both the thermal population of the Stark components of Ln(III) and the Ln(III)-Cu(II) interaction; the latter are only governed by the thermal population of the Ln(III) Stark components. It has been confirmed that the Gd(III)-Cu(II) interaction was ferromagnetic, and it was found that the Tb(III)-Cu(II) and Dy(III)-Cu(II) interactions were ferromagnetic as well. The Tm(III)-Cu(II) interaction might also be ferromagnetic; the situation, however, is uncertain. On the other hand, in all other cases the Ln(III)-Cu(II) interaction is not ferromagnetic; it is either not detectable by the magnetic technique or antiferromagnetic. The difference between Dy(III)-Cu(II) (ferromagnetic) and Ho(III)-Cu(II) (not ferromagnetic) is particularly striking. These findings have been discussed.