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Structure and Magnetization Dynamics of Dy−Fe and Dy−Ru Bonded Complexes
Authors:Corey P. Burns  Xin Yang  Joshua D. Wofford  Dr. Nattamai S. Bhuvanesh  Prof. Michael B. Hall  Prof. Michael Nippe
Affiliation:Department of Chemistry, Texas A&M University, College Station, TX, USA
Abstract:We present an investigation of isostructural complexes that feature unsupported direct bonds between a formally trivalent lanthanide ion (Dy3+) and either a first‐row (Fe) or a second‐row (Ru) transition metal (TM) ion. The sterically rigid, yet not too bulky ligand PyCp22? (PyCp22?=[2,6‐(CH2C5H3)2C5H3N]2?) facilitates the isolation and characterization of PyCp2Dy?FeCp(CO)2 ( 1 ; d(Dy–Fe)=2.884(2) Å) and PyCp2Dy?RuCp(CO)2 ( 2 ; d(Dy–Ru)=2.9508(5) Å). Computational and spectroscopic studies suggest strong TM→Dy bonding interactions. Both complexes exhibit field‐induced slow magnetic relaxation with effectively identical energy barriers to magnetization reversal. However, in going from Dy?Fe to Dy?Ru bonding, we observed faster magnetic relaxation at a given temperature and larger direct and Raman coefficients, which could be due to differences in the bonding and/or spin–phonon coupling contributions to magnetic relaxation.
Keywords:dysprosium  heterometallic complexes  lanthanide–  transition metal bonding  magnetic properties  organometallic chemistry
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