Magneto-Structural Relationship on Strong Exchange Interactions between Chelating Nitroxide Radical and Transition-Metal Spins
Magneto-Structural Relationship on Strong Exchange Interactions between Chelating Nitroxide Radical and Transition-Metal Spins
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DOI：
10.1088/1757-899x/202/1/012002
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发表时间：
2017-05
期刊：
影响因子：
2.8
通讯作者：
A. Okazawa
中科院分区：
文献类型：
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作者：
A. Okazawa
金属自由基方法是发展室温分子磁体最有前途的方法之一。超过室温热能的强磁相互作用对于实现这种令人垂涎的材料至关重要。我们已经开发了2-吡啶基叔丁基氮氧化物（2 pyNO）衍生物作为螯合自由基配体与铜（II）或镍（II）离子。围绕M−O−N− C2 py的扭转角（）是描述结构与金属自由基交换耦合2 J（定义为H = − 2 J <$Si Si +1）之间相关性的有用度量。虽然我们以前报道了这样的磁结构相关性，在本文中，我们更新了图2 J与分为两类：hexacoordinatenickel（II）和铜（II）的配合物。对Cu和Ni两种金属元素，用经验线性关系表示为：2 J/k B = a + B||其中a = 503（112）K和B = -36（3）K deg-1; a = 449（46）K和B = -21.0（17）K deg-1。在后一个图中，我们证实，该关系可以推广为oxoverdazyl和二噻二唑基系统以及2 pyNO系统。基于密度泛函理论的计算结果支持的结果。
To develop room-temperature molecule-based magnets, metal–radical approach is one of the most promising strategies. Strong magnetic interactions beyond a thermal energy of room temperature are essential for achieving such coveted materials. We have developed 2-pyridyl tert-butyl nitroxide (2pyNO) derivatives as a chelating radical ligand with a copper(II) or nickel(II) ion. The torsion angle () around M−O−N−C2py is a useful metric in describing correlation between the structure and metal–radical exchange coupling 2J (defined as H = −2JΣSi Si +1). Although we previously reported such a magneto-structural correlation, in this paper we updated the plot of 2J versus by dividing into two categories: the hexacoordinatenickel(II) and copper(II) complexes. An empirical linear correlation was formulated for both Cu and Ni categories, as 2J/k B = a + b|| with a = 503(112) K and b = –36(3) K deg–1 and with a = 449(46) K and b = –21.0(17) K deg–1, respectively. In the latter plot we confirm that the relationship can be generalized for the oxoverdazyl and dithiadiazolyl systems as well as the 2pyNO systems. The results are supported by the calculations based on the density functional theory.