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Effect of Second-Sphere Interactions on the Magnetic Anisotropy of Lanthanide Single-Molecule Magnets: Electrostatic Interactions and Supramolecular Contacts
journal contribution
posted on 2020-02-25, 18:03 authored by Yolimar Gil, Leonel Llanos, Patricio Cancino, Pablo Fuentealba, Andrés Vega, Evgenia Spodine, Daniel AravenaTo
study how second-sphere interactions affect single-molecule
magnet (SMM) properties of mononuclear lanthanide systems, two dysprosium(III)
complexes [Dy(N-NCS)3(H2O)5]·0.45(KSCN)(18-crown-6) (1) and [Dy(NO3)2(N-NCS)3(H2O)]·(H2O)(NH4)22(18-crown-6)
(2) were synthesized and characterized by single-crystal
X-ray diffraction, ac, dc magnetometry, and multireference ab initio
calculations. For 1, DyIII complexes are encapsulated
between two crown ether molecules, while crown ether molecules and
DyIII complexes crystallize in separate rows for 2. Ab initio calculations indicate that encapsulation is detrimental
for magnetic anisotropy in the case of 1. This effect
is related to a mismatch of the anisotropy axis of the DyIII complex and the symmetry axis of the encapsulating crown ether molecules.
Ab initio calculations show that the reorientation of the electrostatic
potential exerted by the crown ethers to a more symmetric position
produces an enhancement of magnetic anisotropy. We tested the general
character of this effect by analyzing a reported DyIII complex
encapsulated by crown ether molecules. We also investigated how specific
hydrogen-bond interactions affect magnetic anisotropy and show that
H-bonds can be beneficial or prejudicial for magnetic anisotropy,
depending on their position with respect to the magnetic axis. Our
conclusions give general orientations about tuning intermolecular
interactions to promote single-molecule magnet properties by controlling
electrostatic and supramolecular interactions.
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multireference ab initio calculationsencapsulating crown ether moleculescrown ether moleculessingle-crystal X-ray diffractionAb initio calculations showDy IIIanisotropyLanthanide Single-Molecule MagnetsKSCNinteractionsingle-molecule magnet propertiesSMMAb initio calculationsH 2 ODy III complexesaxisNCS
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