Paddlewheel-type dirhodium (Rh2) complexes with N,N'-bridging ligands such as formamidate ions, which have a single bond within the dinuclear core, are redox-active and adopt four oxidation states (Rh23+,Rh24+, Rh25+,and Rh26+) depending on the kinds of coordination ligands at the equatorial and axial positions of the Rh2 bond. N,N'-bridging ligands possess a strong r-donating ability, which significantly induces the destabilization of p*(Rh2) and d*(Rh2) orbitals, and strongly coordinate to the metal center compared with other O,O'- and N,O-bridging ligands. Therefore, Rh2 complexes with N,N'-bridging ligands show unique near-infrared absorption and electrochemical properties. This review summarizes the syn-thesis, crystal structures, electrochemical behaviors, absorption features, and magnetic properties of paddlewheel-type Rh2 complexes with N,N'-bridging ligands, Rh2(L)4 (L = N,N'-diarylformamidinate, 2-anilinopyridinate, etc.).(c) 2022 Elsevier B.V. All rights reserved.
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