Paramagnetic Metal-Metal Bonded Heterometallic Complexes

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.