Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic4029645
Title: Single-Molecule Magnetism in a Family of {(Co2Dy2III)-Dy-III} Butterfly Complexes: Effects of Ligand Replacement on the Dynamics of Magnetic Relaxation
Authors: Langley, Stuart K
Ungur, Liviu 
Chilton, Nicholas F
Moubaraki, Boujemaa
Chibotaru, Liviu F
Murray, Keith S
Keywords: Science & Technology
Physical Sciences
Chemistry, Inorganic & Nuclear
Chemistry
GROUND-STATE SPINS
NUCLEAR-SPIN
ANISOTROPY
SYMMETRY
CHEMISTRY
CRYSTALS
CLUSTERS
Issue Date: 5-May-2014
Publisher: AMER CHEMICAL SOC
Citation: Langley, Stuart K, Ungur, Liviu, Chilton, Nicholas F, Moubaraki, Boujemaa, Chibotaru, Liviu F, Murray, Keith S (2014-05-05). Single-Molecule Magnetism in a Family of {(Co2Dy2III)-Dy-III} Butterfly Complexes: Effects of Ligand Replacement on the Dynamics of Magnetic Relaxation. INORGANIC CHEMISTRY 53 (9) : 4303-4315. ScholarBank@NUS Repository. https://doi.org/10.1021/ic4029645
Abstract: The synthesis and structural characterization of four related heterometallic complexes of formulas [DyIII2Co III2(OMe)2(teaH)2(O 2CPh)4(MeOH)4](NO3) 2·MeOH·H2O (1a) and [DyIII2CoIII2(OMe)2(teaH) 2(O2CPh)4(MeOH)2(NO 3)2]·MeOH·H2O (1b), [Dy III2CoIII2(OMe)2(dea) 2(O2CPh)4(MeOH)4](NO 3)2 (2), [DyIII2Co III2(OMe)2(mdea)2(O 2CPh)4(NO3)2] (3), and [Dy III2CoIII2(OMe)2(bdea) 2(O2CPh)4(MeOH)4](NO 3)2·0.5MeOH·H2O (4a) and [Dy III2CoIII2(OMe)2(bdea) 2(O2CPh)4(MeOH)2(NO 3)2]·MeOH·1.5H2O (4b) are reported (teaH3 = triethanolamine, deaH2 = diethanolamine, mdeaH2 = N-methyldiethanolamine, and bdeaH2 = N-n-butyldiethanolamine). Compounds 1 (- 1a and 1b) and 4 (- 4a and 4b) both display two unique molecules within the same crystal and all compounds display a butterfly type core, with the DyIII ions occupying the central body positions and the diamagnetic CoIII ions the outer wing-tip sites. Compounds 1-4 were investigated via direct current and alternating current magnetic susceptibility measurements, and it was found that each complex displayed single-molecule magnet (SMM) behavior. All four compounds display unique coordination and geometric environments around the DyIII ions and it was found that each displays a different anisotropy barrier. Ab initio calculations were performed on 1-4 and these determined the low lying electronic structure of each DyIII ion and the magnetic interactions for each cluster. It was found that there was a strong correlation between the calculated energy gap between the ground and first excited states of the single-ion ligand-field split DyIII levels and the experimentally observed anisotropy barrier. Furthermore, the transverse g factors found for the Dy III ions, defining the tunnelling rates within the ground Kramers doublets, are largest for 1, which agrees with the experimental observation of the shortest relaxation time in the high-temperature domain for this complex. The magnetic exchange between the DyIII ions revealed overall antiferromagnetic interactions for each compound, derived from the dominant dipolar exchange resulting in nonmagnetic ground states for 1-4. The diamagnetic ground states coupled with small tunneling gaps resulted in quantum tunneling time scales at zero field of between 0.1 and >1.5 s. © 2014 American Chemical Society.
Source Title: INORGANIC CHEMISTRY
URI: https://scholarbank.nus.edu.sg/handle/10635/228701
ISSN: 0020-1669
1520-510X
DOI: 10.1021/ic4029645
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