Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II)

Abstract

The divalent metallocene complexes Ln(Cp^iPr5)₂ (Ln = Tb, Dy) were synthesized through the KC₈ reduction of Ln(Cp^iPr5)₂I intermediates and represent the first examples of neutral, linear metallocenes for these elements. X-ray diffraction analysis, density functional theory calculations, and magnetic susceptibility measurements indicate a 4f^<i>n</i>5d¹ electron configuration with strong s/d mixing that supports the linear coordination geometry. A comparison of the magnetic relaxation behavior of the two divalent metallocenes relative to salts of their trivalent counterparts, [Ln(Cp^iPr5)₂][B(C₆F₅)₄], reveals that lanthanide reduction has opposing effects for dysprosium and terbium, with magnetic relaxation times increasing from Tb^III to Tb^II and decreasing from Dy^III to Dy^II. The impact of this effect is most notably evident for Tb(Cp^iPr5)₂, which displays an effective thermal barrier to magnetic relaxation of 1205 cm^-1 and a 100-s blocking temperature of 52 K, the highest values yet observed for any nondysprosium single-molecule magnet.