Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic302735j
Title: By Design: A Macrocyclic 3d-4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization
Authors: Feltham, Humphrey LC
Clerac, Rodolphe
Ungur, Liviu 
Chibotaru, Liviu F
Powell, Annie K
Brooker, Sally
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
COMPLEXES
TETRANUCLEAR
ANISOTROPY
CLUSTERS
BEHAVIOR
FAMILY
ION
Issue Date: 18-Mar-2013
Publisher: AMER CHEMICAL SOC
Citation: Feltham, Humphrey LC, Clerac, Rodolphe, Ungur, Liviu, Chibotaru, Liviu F, Powell, Annie K, Brooker, Sally (2013-03-18). By Design: A Macrocyclic 3d-4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization. INORGANIC CHEMISTRY 52 (6) : 3236-3240. ScholarBank@NUS Repository. https://doi.org/10.1021/ic302735j
Abstract: Rational modification of the equatorially bound tetranucleating macrocycle in the previously reported SMM complex of the propylene linked macrocycle [CuII3TbIII(LPr)](NO 3)2, to a new butylene linked analogue, is shown to tune the ligand field imposed on the encapsulated CuII3Tb III 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, [CuII3TbIII(L Bu)(NO3)2(MeOH)(H2O)](NO 3)·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, Zn 3Tb(LBu)(NO3)3·MeOH· H2O·DMF and [Cu3La(LBu)(NO 3)2(MeOH)(H2O)2](NO 3)·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. © 2013 American Chemical Society.
Source Title: INORGANIC CHEMISTRY
URI: https://scholarbank.nus.edu.sg/handle/10635/228844
ISSN: 00201669
1520510X
DOI: 10.1021/ic302735j
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