Metal–Metal Single Bonds with the Magnetic Anisotropy of Quadruple Bonds: A Systematic Series of Heterobimetallic Bismuth(II)–Rhodium(II) Formamidinate Complexes |
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Authors: | Dr. Travis L. Sunderland Dr. John F. Berry |
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Affiliation: | Department of Chemistry, University of Wisconsin-Madison, WI, USA |
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Abstract: | The first set of five heterobimetallic MM′(form)4 (form=formamidinate) complexes containing a BiRh core has been successfully synthesized. The Bi?Rh bond lengths 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 approximately 700 mV and showing a strong correlation to remote ligand substitution. Visible spectroscopy showed two features for complexes 1 – 5 at approximately 459 and 551 nm, unique to BiRh paddlewheel complexes that are attributed to LMCT bands into the Bi?Rh σ* orbital. The large spin–orbit coupling (SOC) of Bi creates a massive Bi?Rh magnetic anisotropy, Δχ, approximately ?4800×10?36 m3molecule?1, which is the largest value reported for any single bond to date. |
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Keywords: | bismuth heterobimetallic complexes magnetic anisotropy metal– metal bonds rhodium |
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