title: Influence of an inner-sphere K+ ion on the magnetic behavior of N2(3-) radical-bridged dilanthanide complexes isolated using an external magnetic field.
abstract: The synthesis and full magnetic characterization of a new series of N2(3-) radical-bridged lanthanide complexes [{(R2N)2(THF)Ln}2(μ3-η(2):η(2):η(2)-N2)K] [1-Ln; Ln = Gd, Tb, Dy; NR2 = N(SiMe3)2] are described for comprehensive comparison with the previously reported series [K(18-crown-6)(THF)2]{[(R2N)2(THF)Ln]2(μ-η(2):η(2)-N2)} (2-Ln; Ln = Gd, Tb, Dy). Structural characterization of 1-Ln crystals grown with the aid of a Nd2Fe13B magnet reveals inner-sphere coordination of the K(+) counterion within 2.9 Å of the N2(3-) bridge, leading to bending of the planar Ln-(N2(3-))-Ln unit present in 2-Ln. Direct current (dc) magnetic susceptibility measurements performed on 1-Gd reveal antiferromagnetic coupling between the Gd(III) centers and the N2(3-) radical bridge, with a strength matching that obtained previously for 2-Gd at J ∼ -27 cm(-1). Unexpectedly, however, a competing antiferromagnetic Gd(III)-Gd(III) exchange interaction with J ∼ -2 cm(-1) also becomes prominent, dramatically changing the magnetic behavior at low temperatures. Alternating current (ac) magnetic susceptibility characterization of 1-Tb and 1-Dy demonstrates these complexes to be single-molecule magnets under zero applied dc field, albeit with relaxation barriers (Ueff = 41.13(4) and 14.95(8) cm(-1), respectively) and blocking temperatures significantly reduced compared to 2-Tb and 2-Dy. These differences are also likely to be a result of the competing antiferromagnetic Ln(III)-Ln(III) exchange interactions of the type quantified in 1-Gd.
authors.affiliation: Department of Chemistry, University of California , Berkeley, California 94720-1460, United States.
authors.forename: Katie R
authors.initials: KR
authors.lastname: Meihaus
authors.forename: Jordan F
authors.initials: JF
authors.lastname: Corbey
authors.forename: Ming
authors.initials: M
authors.lastname: Fang
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Ziller
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Long
authors.forename: William J
authors.initials: WJ
authors.lastname: Evans