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- Title
Influence of the Coordinated Transition Metal Ion on Magnetic Relaxation of Lanthanide Based Complexes with Imino Nitroxide Biradical Ligands.
- Authors
Xi, Lu; Jin, Chaoyi; Song, Hongwei; Wang, Xiaotong; Xie, Junfang; Ma, Yue; Tang, Jinkui; Li, Licun
- Abstract
In spite of achievement of a lot of Ln‐radical SMMs, how to improve magnetic behavior of Ln‐radical system remains challenging. Here, two series of Ln‐radical complexes have successfully been built using an imino nitroxide biradical, namely, [Ln2(hfac)6(ImPhPyobis)2] (LnIII=Gd 1, Tb 2, Dy 3) and [Ln2Cu2(hfac)10(ImPhPyobis)2] (LnIII=Gd 4, Dy 5; hfac=hexafluoroacetylacetonate and ImPhPyobis=5‐(4‐oxypyridinium‐1‐yl)‐1,3‐bis(1'‐oxyl‐4',4',5',5'‐tetramethyl‐4,5‐hydro‐1H‐imidazol‐2‐yl)benzene). For these biradical‐metal complexes, two imino nitroxide biradicals bind two Ln(III) ions via their oxygen atoms coming from 4‐oxypyridinium units to produce a binuclear {Ln2O2} unit. Those imino nitroxide groups are free for complexes 1–3, however one of imino nitroxide groups of the biradical is ligated to the copper(II) ion for complexes 4 and 5. The distinct magnetic relaxation behaviors are observed for two Dy derivatives, as revealed by ac magnetic studies: complex 3 presents one magnetic process with the effective energy barrier(Ueff) of 74.0 K while complex 5 exhibits dual relaxation processes with Ueff values for the fast‐ and slow‐relaxation being 20.2 K and 30.9 K, respectively, which implies that the second coordination sphere of Dy ion plays a critical role for magnetic relaxation.
- Subjects
NITROXIDES; MAGNETIC relaxation; TRANSITION metals; TRANSITION metal ions; RARE earth metals; MAGNETIC ions; IMINO group; LIGANDS (Chemistry)
- Publication
Chemistry - A European Journal, 2022, Vol 28, Issue 65, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202202239