Magneto-structural correlations in dirhenium( iv ) complexes possessing magnetic pathways with even or odd numbers of atoms
Magneto-structural correlations in dirhenium( iv ) complexes possessing magnetic pathways with even or odd numbers of atoms
复制标题
具有偶数或奇数原子磁路的二铼( iv )配合物的磁结构相关性
DOI：
10.1039/c7dt02612a
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发表时间：
2017
影响因子：
4
通讯作者：
Pedersen A
中科院分区：
文献类型：
--
作者：
Pedersen A
在 ReIV 化学中使用吡嗪 (pyz)、嘧啶 (pym) 和 s-三嗪 (triz) 配体可分离出一系列通式 (NBu4)2[(ReX5)2(μ-L)] 的配合物（L = pyz，X = Cl (1) 或 Br (2)；L = pym，X = Br (3)；L = triz，X = Br (4))。 1-4 是双核化合物，其中两个五卤铼 (IV) 片段通过双齿 pyz、pym 和 triz 配体连接。变温磁测量与详细的理论研究相结合，揭示了潜在的磁结构相关性，其中金属离子之间的交换性质由介入原子的数量决定。也就是说，存在的自旋极化机制表明奇数和偶数原子分别有利于铁磁（F）和反铁磁（AF）交换相互作用。因此，虽然 1 和 2 中的 pyz 配体介导 AF 偶联，但 3 和 4 中的 pym 和 triz 配体促进 F 相互作用。
The employment of pyrazine (pyz), pyrimidine (pym) and s-triazine (triz) ligands in ReIV chemistry leads to the isolation of a family of complexes of general formula (NBu4)2[(ReX5)2(μ-L)] (L = pyz, X = Cl (1) or Br (2); L = pym, X = Br (3); L = triz, X = Br (4)). 1–4 are dinuclear compounds where two pentahalorhenium(IV) fragments are connected by bidentate pyz, pym and triz ligands. Variable-temperature magnetic measurements, in combination with detailed theoretical studies, uncover the underlying magneto-structural correlation whereby the nature of the exchange between the metal ions is dictated by the number of intervening atoms. That is, the spin-polarization mechanism present dictates that odd and even numbers of atoms favour ferromagnetic (F) and antiferromagnetic (AF) exchange interactions, respectively. Hence, while the pyz ligand in 1 and 2 mediates AF coupling, the pym and triz ligands in 3 and 4 promote F interactions.