Please use this identifier to cite or link to this item: https://doi.org/10.1002/chem.201801523
Title: Exchange Interactions Switch Tunneling: A Comparative Experimental and Theoretical Study on Relaxation Dynamics by Targeted Metal Ion Replacement
Authors: Tian, Haiquan
Ungur, Liviu 
Zhao, Lang
Ding, Shuai
Tang, Jinkui
Chibotaru, Liviu F
Keywords: Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
ab initio calculations
lanthanides
magnetic properties
manganese
N,O ligands
SINGLE-MOLECULE MAGNET
SPIN-LATTICE-RELAXATION
SPACE SCF METHOD
ZERO-FIELD
NANO-MAGNETS
BASIS-SETS
COMPLEXES
BEHAVIOR
MAGNETIZATION
ANISOTROPY
Issue Date: 11-Jul-2018
Publisher: WILEY-V C H VERLAG GMBH
Citation: Tian, Haiquan, Ungur, Liviu, Zhao, Lang, Ding, Shuai, Tang, Jinkui, Chibotaru, Liviu F (2018-07-11). Exchange Interactions Switch Tunneling: A Comparative Experimental and Theoretical Study on Relaxation Dynamics by Targeted Metal Ion Replacement. CHEMISTRY-A EUROPEAN JOURNAL 24 (39) : 9928-9939. ScholarBank@NUS Repository. https://doi.org/10.1002/chem.201801523
Abstract: The magnetic relaxation and magnetization blocking barriers of tailor-made homo- and heterodinuclear compounds [Dy2(opch)2(OAc)2(H2O)2]⋅MeOH (1) and [DyMn(opch)2(OAc)(MeOH)(H2O)2] (2), where H2opch is (E)-N′-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide, were systematically investigated and the change in single-molecule magnet behavior originating from targeted replacement of one dysprosium site in the Dy2 compound with manganese was elucidated through a combination of experimental and theoretical studies. A detailed comparative study on these closely related model compounds revealed remarkable changes of the crystal-field splitting and anisotropy of the Dy site and the total exchange spectrum due to the replacement of Dy by Mn. The blocking barriers of these two compounds, which explain their different relaxation behaviors, were analyzed. The two Ising doublets arising from the magnetic interaction in the case of 1 are strongly uniaxial, with tunneling splittings smaller than 10−6 cm−1, and this leads to magnetic relaxation at temperatures exceeding the exchange energy (2.14 cm−1), which involves transition via the excited states corresponding to local transitions on the excited doublet at the Dy site. The third and fourth exchange doublets in 2 (located at 2.16 and 3.25 cm−1, respectively) show much larger tunneling splittings (of 10−4 and 10−3 cm−1, respectively), and thus open an important path for magnetic relaxation.
Source Title: CHEMISTRY-A EUROPEAN JOURNAL
URI: https://scholarbank.nus.edu.sg/handle/10635/228693
ISSN: 09476539
15213765
DOI: 10.1002/chem.201801523
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