TY - JOUR T1 - Metal-Metal Single Bonds with the Magnetic Anisotropy of Quadruple Bonds: A Systematic Series of Heterobimetallic Bismuth(II)-Rhodium(II) Formamidinate Complexes JF - Chemistry - A European Journal Y1 - 2016 A1 - Sunderland, Travis L. A1 - Berry, J.F. AB -

The first set of five heterobimetallic MM'(form)4 (form = formamidinate) complexes has been successfully synthesized containing a BiRh core. The Bi-Rh bond distances lie between 2.5196(6) and 2.572[2] Å, consistent with Bi-Rh single bonds. All complexes have rich electrochemistry, with the [BiRh]4+/5+ redox couples spanning ~ 700 mV and showing a strong correlation to remote ligand substitution. Visible spectroscopy shows two features for complexes 1 - 5 at ~ 459 and ~ 551 nm, unique to BiRh paddlewheel complexes that are attributed to LMCT bands into the Bi-Rh * orbital. The large spin-orbit coupling (SOC) of Bi creates a massive Bi-Rh magnetic anisotropy, Δ, ~ -4800 x 10-36 m3/molecule, which is the largest value reported for any single bond to date.

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