Chipman Jill A, Berry John F
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison Wisconsin 53706, United States.
Chem Rev. 2020 Mar 11;120(5):2409-2447. doi: 10.1021/acs.chemrev.9b00540. Epub 2020 Feb 11.
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.
在过去10到15年里，具有顺磁性异金属-金属键的多金属配位络合物的设计、合成及性质方面取得了显著进展。已探索了几类化合物，包括异双金属化合物、具有线性或三角形几何结构的异三金属化合物、含有三个以上金属原子线性阵列的离散分子化合物以及具有异金属-金属键合主链的配位聚合物。在本综述中，我们关注用于制备这些化合物的合成方法、它们的结构特征、磁性质和电子结构。关于金属-金属键距离，我们利用形式短程比（FSR）来比较不同大小的各种金属原子之间的键距离。这些化合物的磁性质可以通过将古迪纳夫-金森规则扩展到两个磁性离子通过第三个金属原子相互作用的情况来描述。在描述电子结构时，我们关注电子是否能够在异金属键之间离域，这有助于对顺磁性异金属分子导线中的单分子电导测量进行合理化解释和预测。
