cobalt ii

ii ions

coordination chemistry

magnetic relaxation

copper ii

magnetic susceptibility

received online clicking

Chemical Reviews

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.

Paramagnetic Metal–Metal Bonded Heterometallic Complexes