Ab Initio Prediction of High-Temperature Magnetic Relaxation Rates in Single-Molecule Magnets

Reta, Daniel; Kragskow, Jon G. C.; Chilton, Nicholas F.

doi:10.1021/jacs.1c01410

Cited by 138 publications

(246 citation statements)

References 42 publications

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“…[3][4][5][6][7][8][9][10] The enhancement of T B as high as 80 K in "Dysprocenium" complexes was an important breakthrough, replenishing the hope for potential applications in the information storage devices. [11][12][13][14][15] Among others, the important bottlenecks that are likely to hamper the futuristic application of these SMMs are (i) enhancing the blocking temperature beyond 80 K (ii) obtaining molecules that are stable under ambient conditions so that fabrication can be attempted (iii) retaining their intriguing magnetic properties upon fabrication -many best transition metal SMMs failed these criteria. [16][17][18][19][20][21] To address the first challenge, among other strategies that could help enhance the barrier height/blocking temperature, is to quench quantum tunnelling of magnetisation (QTM), which is prevalent at low temperatures.…”

Section: Introductionmentioning

confidence: 99%

Attaining record-high magnetic exchange, magnetic anisotropy and blocking barriers in dilanthanofullerenes

Dey

Rajaraman

2021

Chem. Sci.

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Section: Introductionmentioning

confidence: 99%

Attaining record-high magnetic exchange, magnetic anisotropy and blocking barriers in dilanthanofullerenes

Dey

Rajaraman

2021

Chem. Sci.

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“…This quantifies the difference in the magnetic response when an external magnetic field is applied in different directions relative to the molecule. One caveat is that, although high-level ab initio calculations are able to calculate both magnetic anisotropy (Neese et al, 2019) and, recently, magnetic relaxation properties (Reta et al, 2021), such calculations are experts tools, and we are still not able to predict the exact magnetic properties of such compounds from a simple set of rules.…”

Section: Introductionmentioning

confidence: 99%

Quantifying magnetic anisotropy using X-ray and neutron diffraction

Klahn¹,

Damgaard‐Møller²,

Krause³

et al. 2021

IUCrJ

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In this work, the magnetic anisotropy in two iso-structural distorted tetrahedral Co(II) complexes, CoX 2tmtu2 [X = Cl(1) and Br(2), tmtu = tetramethylthiourea] is investigated, using a combination of polarized neutron diffraction (PND), very low-temperature high-resolution synchrotron X-ray diffraction and CASSCF/NEVPT2 ab initio calculations. Here, it was found consistently among all methods that the compounds have an easy axis of magnetization pointing nearly along the bisector of the compression angle, with minute deviations between PND and theory. Importantly, this work represents the first derivation of the atomic susceptibility tensor based on powder PND for a single-molecule magnet and the comparison thereof with ab initio calculations and high-resolution X-ray diffraction. Theoretical ab initio ligand field theory (AILFT) analysis finds the d xy orbital to be stabilized relative to the d xz and d yz orbitals, thus providing the intuitive explanation for the presence of a negative zero-field splitting parameter, D, from coupling and thus mixing of d xy and d x 2 − y 2 . Experimental d-orbital populations support this interpretation, showing in addition that the metal–ligand covalency is larger for Br-ligated 2 than for Cl-ligated 1.

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“…On the other hand, the decreasing trend of the power n may be attributed to the rising of the energies of critical vibrational modes engaged in the magnetic relaxation going within the series of 1•MeCN, 1•AcrCN, 1•PrCN, and 1•MalCN. However, the detection of such critical phonon modes is a very difficult task and stays beyond the scope of this article [73]. The variation of the power n of the Raman relaxation results in the variation of effective energy barriers, U eff , obtained from the Arrhenius-type plots (Equation ( 2), Table 1).…”

Section: Magnetic Propertiesmentioning

confidence: 99%

Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization

et al. 2021

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One of the pathways toward luminescent single-molecule magnets (SMMs) is realized by the self-assembly of lanthanide(3+) ions with cyanido transition metal complexes. We report a novel family of emissive SMMs, {YbIII(4-pyridone)4[FeII(phen)2(CN)2]2}(CF3SO3)3·solv (solv = 2MeCN, 1·MeCN; 2AcrCN, 1·AcrCN; 2PrCN, 1·PrCN; 2MalCN·1MeOH; 1·MalCN; MeCN = acetonitrile, AcrCN = acrylonitrile, PrCN = propionitrile, MalCN = malononitrile). They are based on paramagnetic YbIII centers coordinating diamagnetic [FeII(phen)2(CN)2] metalloligands but differ in the nitrile solvents of crystallization. They exhibit a field-induced slow magnetic relaxation dominated by a Raman process, without an Orbach relaxation as indicated by AC magnetic data and the ab initio calculations. The Raman relaxation is solvent-dependent as represented by the power “n” of the BRamanTn contribution varying from 3.07(1), to 2.61(1), 2.37(1), and 1.68(4) for 1·MeCN, 1·PrCN, 1·AcrCN, and 1·MalCN, respectively, while the BRaman parameter adopts the opposite trend. This was correlated with the variation of phonon modes schemes, including the number of available vibrational modes and their energies, dependent on the increasing complexity of the applied nitrile. 1·MeCN and 1·MalCN show the additional T-independent relaxation assignable to dipole-dipole interactions as confirmed by its suppression in 1·AcrCN and 1·PrCN revealing longer Yb–Yb distances and the disappearance in the LuIII-diluted 1·MeCN@Lu. All compounds exhibit YbIII–centered near-infrared photoluminescence sensitized by organic ligands.

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Ab Initio Prediction of High-Temperature Magnetic Relaxation Rates in Single-Molecule Magnets

Abstract: download file view on ChemRxiv Long_Layfield.docx (1.12 MiB) download file view on ChemRxiv Long_Layfield_SI.docx (5.82 MiB) Ab initio prediction of high-temperature magnetic relaxation rates in single-molecule magnets

Cited by 138 publications

References 42 publications

Attaining record-high magnetic exchange, magnetic anisotropy and blocking barriers in dilanthanofullerenes

Attaining record-high magnetic exchange, magnetic anisotropy and blocking barriers in dilanthanofullerenes

Quantifying magnetic anisotropy using X-ray and neutron diffraction

Near-Infrared Emissive Cyanido-Bridged {YbFe2} Molecular Nanomagnets Sensitive to the Nitrile Solvents of Crystallization

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