Single-Ion Magnetism in a Three-Dimensional Thiocyanate-Bridged Dysprosium(III) Framework

Abstract

New three-dimensional (3D) lanthanide framework compounds supported by bridging thiocyanate ligand and K+ cations, K4[Ln(NCS)4(H2O)4](NCS)3(H2O)2(1: Ln = Dy, 2: Ln = Tb, 3: Ln = Gd) have been synthesized. A single-crystal X-ray diffraction study showed that all three compounds were isostructural and crystallized in the I 2/a space group. The K+ ion form 2D layers with thiocyanates which are further linked by [Ln(NCS)4(H2O)4]- complexes and additional thiocyanate ions to generate an interesting 3D framework structure. Compound 1 shows slow magnetic relaxation behavior under a zero direct current (DC) field, indicating that 1 behaves as a single-ion magnet (SIM). As estimated from AC magnetic measurements, the effective energy barrier for spin reversal in 1 was Ueff = 42 cm–1. Slow relaxation of magnetization under a small external DC field was also detected for 2 and 3 at 1.8 K.

Single-ion magnetism behaviors in lanthanide(iii) based coordination frameworks

“…In a recent work by Yamashita and coworkers, three new Dy 3+ , Tb 3+ and Gd 3+ based coordination frameworks were reported, which are linked by inorganic SCN ligands and K + ions. 95 By examining the magnetic properties (Fig. 8), compound 20 was observed to show SMM properties with slow magnetic relaxation behavior under zero dc field and a U eff of 60 K.…”

“…In contrast, other Ln( iii )-frameworks, such as Gd( iii ) or Tb( iii ), typically exhibit multiple Debye relaxations and a lack of slow magnetization under a zero direct current (DC) field. 95 As a result, structures of Dy( iii )-frameworks have been reviewed and described in greater detail herein.…”