Boosting axiality in stable high-coordinate Dy(<scp>iii</scp>) single-molecule magnets

Canaj, Angelos B.; Singh, Mukesh Kumar; Martí, Emma Regincós; Damjanović, Marko; Wilson, Claire; Céspedes, Oscar; Wernsdorfer, Wolfgang; Rajaraman, Gopalan; Murrie, Mark

doi:10.1039/c9cc00965e

Cited by 59 publications

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References 48 publications

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“…This complex was previously A c c e p t e d M a n u s c r i p t shown to exhibit slow magnetic relaxation at high temperatures as a result of strong axial magnetic anisotropy generated by a short Dy-( 1 -F) bond. 27 Exchange of the equatorial pyridine ligands in this compound with a ditopic photoactive bispyridyl dithienylethene (DTE) ligand 28 yields infinite chains of single-molecule magnets that undergo a single-crystal-to-single-crystal transformation upon visible irradiation and exhibit unprecedented photomodulation of magnetic hysteresis behavior at temperatures as high as 4 K.…”

Section: Introductionmentioning

confidence: 99%

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets

et al. 2019

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A one-dimensional coordination solid is synthesized by reaction of a bispyridyl dithienylethene (DTE) photochromic unit with the highly anisotropic dysprosium-based single-molecule magnet [Dy(Tppy)F(pyridine)2]PF6. Slow magnetic relaxation characteristics are retained in the chain compound, 1c, and photoisomerization of the bridging DTE ligand induces a single-crystal-to-single-crystal transformation that can be monitored using photocrystallography. Notably, the resulting chain compound 1o exhibits faster low-temperature relaxation than 1c, which is apparent in magnetic hysteresis data collected for both compounds as high as 4 K. Ab initio calculations suggest that this photomodulation of the magnetic relaxation behavior is due to crystal packing changes rather than changes to the crystal field splitting upon ligand isomerization.

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Section: Introductionmentioning

confidence: 99%

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets

et al. 2019

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“…The first generation of SMMs was based on transition-metal complexes [ 3 , 4 ]. Trivalent lanthanides, Ln(III)s, came into the scientific scene of the SMM area in 2003 with the mononuclear, double-decker complexes [Ln III (pc) 2 ]¯ (Ln = Tb, Dy; pc 2− = the phthalocyanine dianion) [ 5 ], and they are currently protagonists [ 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 ] in the interdisciplinary field of molecular magnetism. The latest scientific breakthrough was the synthesis of [(η 5 − cp*)Dy(η 5 − cp iPr5 )][B(C 6 F 5 ) 4 ], where cp* is the pentamethylcyclopentadienyl(−1) group and cp iPr5 is the penta-iso-propylcyclopentadienyl(−1) ligand [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Dinuclear Lanthanide(III) Complexes from the Use of a Ligand Derived from 2-Acetylpyridine and Picolinoylhydrazide: Synthetic, Structural and Magnetic Studies

et al. 2020

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A family of four Ln(III) complexes has been synthesized with the general formula [Ln2(NO3)4(L)2(S)] (Ln = Gd, Tb, Er, and S = H2O; 1, 2 and 4, respectively/Ln = Dy, S = MeOH, complex 3), where HL is the flexible ditopic ligand N’-(1-(pyridin-2-yl)ethylidene)pyridine-2-carbohydrazide. The structures of isostructural MeOH/H2O solvates of these complexes were determined by single-crystal X-ray diffraction. The two LnIII ions are doubly bridged by the deprotonated oxygen atoms of two “head-to-head” 2.21011 (Harris notation) L¯ ligands, forming a central, nearly rhombic {LnIII2(μ-OR)2}4+ core. Two bidentate chelating nitrato groups complete a sphenocoronal 10-coordination at one metal ion, while two bidentate chelating nitrato groups and one solvent molecule (H2O or MeOH) complete a spherical capped square antiprismatic 9-coordination at the other. The structures are critically compared with those of other, previously reported metal complexes of HL or L¯. The IR spectra of 1–4 are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The f-f transitions in the solid-state (diffuse reflectance) spectra of the Tb(III), Dy(III), and Er(III) complexes have been fully assigned in the UV/Vis and near-IR regions. Magnetic susceptibility studies in the 1.85–300 K range reveal the presence of weak, intramolecular GdIII∙∙∙GdIII antiferromagnetic exchange interactions in 1 [J/kB = −0.020(6) K based on the spin Hamiltonian Ĥ = −2J(ŜGd1∙ ŜGd2)] and probably weak antiferromagnetic LnIII∙∙∙LnIII exchange interactions in 2–4. Ac susceptibility measurements in zero dc field do not show frequency dependent out-of-phase signals, and this experimental fact is discussed for 3 in terms of the magnetic anisotropy axis for each DyIII center and the oblate electron density of this metal ion. Complexes 3 and 4 are Single-Molecule Magnets (SMMs) and this behavior is optimally observed under external dc fields of 600 and 1000 Oe, respectively. The magnetization relaxation pathways are discussed and a satisfactory fit of the temperature and field dependencies of the relaxation time τ was achieved considering a model that employs Raman, direct, and Orbach relaxation mechanisms.

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“…cyclopentadienyl (Cp) anionic ligands), have generated organometallic compounds with impressive blocking temperatures showing coercivity up to 30 K, 9 48 K, 10 55 K, 11 60 K, 12 66 K 13 and 80 K. 14 Additionally, a unique family of Ln-SMMS are the endohedral metallofullerenes (EMFS). 15 We have explored how the ligand electronics can tune SMM properties 5,7,16,17 and recently first introduced a blueprint for engineering strong uniaxial magnetic anisotropy for Dy(III) ions in a hexagonal bipyramidal geometry, 7 boosting the magnetisation reversal barrier from B50 K 18 to B1100 K, by using the macrocyclic ligand L N6 (Scheme 1 left). Implementing further the flexibility of our synthetic approach towards the engineering of new quasi-D nh systems, we demonstrate the isolation of a new Single-Ion Magnet (SIM) with pentagonal bipyramidal geometry, [Dy III (L N5 )(Ph 3 SiO) 2 ](BPh 4 )ÁCH 2 Cl 2 (1).…”

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confidence: 99%

Engineering macrocyclic high performance pentagonal bipyramidal Dy(iii) single-ion magnets

et al. 2020

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Boosting axiality in stable high-coordinate Dy(iii) single-molecule magnets

Abstract: A combined synthetic, structural, magnetic and computational study gives insight into improving the single-molecule magnet behaviour of stable high-coordinate Dy(iii) complexes.

Cited by 59 publications

References 48 publications

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets

Hysteresis Photomodulation via Single-Crystal-to-Single-Crystal Isomerization of a Photochromic Chain of Dysprosium Single-Molecule Magnets

Asymmetric Dinuclear Lanthanide(III) Complexes from the Use of a Ligand Derived from 2-Acetylpyridine and Picolinoylhydrazide: Synthetic, Structural and Magnetic Studies

Engineering macrocyclic high performance pentagonal bipyramidal Dy(iii) single-ion magnets

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