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      Six-Coordinate Lanthanide Complexes: Slow Relaxation of Magnetization in the Dysprosium(III) Complex

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          Abstract

          A series of six-coordinate lanthanide complexes {(H3O)[Ln(NA)2]⋅H2O}n (H2NA=5-hydroxynicotinic acid; Ln=Gd(III) (1⋅Gd); Tb(III) (2⋅Tb); Dy(III) (3⋅Dy); Ho(III) (4⋅Ho)) have been synthesized from aqueous solution and fully characterized. Slow relaxation of the magnetization was observed in 3⋅Dy. To suppress the quantum tunneling of the magnetization, 3⋅Dy diluted by diamagnetic Y(III) ions was also synthesized and magnetically studied. Interesting butterfly-like hysteresis loops and an enhanced energy barrier for the slow relaxation of magnetization were observed in diluted 3⋅Dy. The energy barrier (Δ(τ)) and pre-exponential factor (τ0) of the diluted 3⋅Dy are 75 K and 4.21×10(-5) s, respectively. This work illustrates a successful way to obtain low-coordination-number lanthanide complexes by a framework approach to show single-ion-magnet-like behavior.

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          Lanthanide double-decker complexes functioning as magnets at the single-molecular level.

          Double-decker phthalocyanine complexes with Tb3+ or Dy3+ showed slow magnetization relaxation as a single-molecular property. The temperature ranges in which the behavior was observed were far higher than that of the transition-metal-cluster single-molecule magnets (SMMs). The significant temperature rise results from a mechanism in the relaxation process different from that in the transition-metal-cluster SMMs. The effective energy barrier for reversal of the magnetic moment is determined by the ligand field around a lanthanide ion, which gives the lowest degenerate substate a large |Jz| value and large energy separations from the rest of the substates in the ground-state multiplets.
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            Bond-valence parameters for solids

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              Lanthanide single-molecule magnets.

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                Author and article information

                Journal
                Chemistry - A European Journal
                Chem. Eur. J.
                Wiley
                09476539
                November 24 2014
                November 24 2014
                October 08 2014
                : 20
                : 48
                : 15975-15980
                Article
                10.1002/chem.201404573
                25297951
                a1577f79-9631-417b-9005-e5b8d01cbb74
                © 2014

                http://doi.wiley.com/10.1002/tdm_license_1.1

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