Title: By Design: A Macrocyclic 3d-4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization
Authors: Feltham, Humphrey L. C
Clerac, Rodolphe
Ungur, Liviu
Chibotaru, Liviu
Powell, Annie K
Brooker, Sally # ×
Issue Date: 2013
Publisher: American Chemical Society
Series Title: Inorganic Chemistry vol:52 issue:6 pages:3236-3240
Abstract: Rational modification of the equatorially bound
tetranucleating macrocycle in the previously reported SMM
complex of the propylene linked macrocycle [CuII
(NO3)2, to a new butylene linked analogue, is shown to tune
the ligand field imposed on the encapsulated CuII
3TbIII cluster.
This results in apical binding of two, rather than one, nitrate
ions to the oblate TbIII ion, giving enhanced uniaxial
anisotropy and SMM properties despite the low symmetry
of the Tb(III) site. The resulting complex, [CuII
(NO3)2(MeOH)(H2O)](NO3)·3H2O, is the first example of a
macrocyclic 3d−4f single-molecule magnet that exhibits quantifiable relaxation of magnetization in zero dc field (Δeff/kB =
19.5(5) K; τ0 = 3.4 × 10−7 s). This SMM complex of this new, larger, tetranucleating macrocycle was prepared by the template
method from the 3:3:3:1 reaction of 1,4-diformyl-2,3-dihydroxybenzene/diaminobutane/copper(II) acetate/terbium(III) nitrate.
Similarly, the analogues, Zn3Tb(LBu)(NO3)3·MeOH·H2O·DMF and [Cu3La(LBu)(NO3)2(MeOH)(H2O)2](NO3)·H2O·DMF,
were prepared in order to facilitate the detailed magnetic analysis. Both copper(II) complexes were also structurally characterized,
confirming the expected binding mode: lanthanide(III) ion in the central O6 pocket, and the three copper(II) ions in the outer
N2O2 pockets.
ISSN: 0020-1669
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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