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Paramagnetic Metal-Metal Bonded Heterometallic Complexes.
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-02-11 , DOI: 10.1021/acs.chemrev.9b00540
Jill A Chipman 1 , John F Berry 1
Affiliation  

Significant progress has been made in the past 10-15 years on the design, synthesis, and properties of multimetallic coordination complexes with heterometallic metal-metal bonds that are paramagnetic. Several general classes have been explored including heterobimetallic compounds, heterotrimetallic compounds of either linear or triangular geometry, discrete molecular compounds containing a linear array of more than three metal atoms, and coordination polymers with a heterometallic metal-metal bonded backbone. We focus in this Review on the synthetic methods employed to access these compounds, their structural features, magnetic properties, and electronic structure. Regarding the metal-metal bond distances, we make use of the formal shortness ratio (FSR) for comparison of bond distances between a broad range of metal atoms of different sizes. The magnetic properties of these compounds can be described using an extension of the Goodenough-Kanamori rules to cases where two magnetic ions interact via a third metal atom. In describing the electronic structure, we focus on the ability (or not) of electrons to be delocalized across heterometallic bonds, allowing for rationalizations and predictions of single-molecule conductance measurements in paramagnetic heterometallic molecular wires.

中文翻译:

顺磁性金属-金属键合杂金属配合物。

在过去的10到15年中,在具有顺磁性的杂金属-金属键的多金属配位配合物的设计,合成和性能方面取得了重大进展。已经探索了几种通用类别,包括杂双金属化合物,线性或三角形几何形状的杂三金属化合物,包含多于三个金属原子的线性阵列的离散分子化合物以及具有杂金属金属-金属键合主链的配位聚合物。我们在本综述中重点介绍了用于获取这些化合物的合成方法,其结构特征,磁性和电子结构。关于金属与金属之间的键距,我们利用形式短路比(FSR)来比较各种大小不同的金属原子之间的键距。这些化合物的磁性可以通过将Goodenough-Kanamori规则扩展到两个磁性离子通过第三金属原子相互作用的情况来描述。在描述电子结构时,我们关注电子在异金属键上的离域能力(或不存在),从而使顺磁异金属分子线中单分子电导测量的合理化和预测成为可能。
更新日期:2020-02-12
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