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Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

ABSTRACT: We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy2(bpm)(fod)6] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the susceptibility tensor was determined by means of cantilever torque magnetometry. An experimental determination of the electronic structure of the lanthanide ion was obtained combining Luminescence, Far Infrared and Magnetic Circular Dichroism spectroscopies. Fitting these energies to the full single ion plus crystal field Hamiltonian allowed determination of the eigenstates and crystal field parameters of a lanthanide complex without symmetry idealization. We then discuss the impact of a stepwise symmetry idealization on the modelling of the experimental data. This result is particularly important in view of the misleading outcomes that are often obtained when the symmetry of lanthanide complexes is idealized.

SUBMITTER: Perfetti M

PROVIDER: S-EPMC6375364 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

Perfetti Mauro M Gysler Maren M Rechkemmer-Patalen Yvonne Y Zhang Peng P Taştan Hatice H Fischer Florian F Netz Julia J Frey Wolfgang W Zimmermann Lucas W LW Schleid Thomas T Hakl Michael M Orlita Milan M Ungur Liviu L Chibotaru Liviu L Brock-Nannestad Theis T Piligkos Stergios S van Slageren Joris J

Chemical science 20181212 7

We present the in-depth determination of the magnetic properties and electronic structure of the luminescent and volatile dysprosium-based single molecule magnet [Dy2(bpm)(fod)6] (Hfod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2'-bipyrimidine). Ab initio calculations were used to obtain a global picture of the electronic structure and to predict possible single molecule magnet behaviour, confirmed by experiments. The orientation of the suscept ...[more]

PMID: 30842867

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Project description:Treatment of the new methanediide-methanide complex [Dy(SCS)(SCSH)(THF)] (1Dy, SCS = {C(PPh2S)2}2-) with alkali metal alkyls and auxillary ethers produces the bis-methanediide complexes [Dy(SCS)2][Dy(SCS)2(K(DME)2)2] (2Dy), [Dy(SCS)2][Na(DME)3] (3Dy) and [Dy(SCS)2][K(2,2,2-cryptand)] (4Dy). For further comparisons, the bis-methanediide complex [Dy(NCN)2][K(DB18C6)(THF)(toluene)] (5Dy, NCN = {C(PPh2NSiMe3)2}2-, DB18C6 = dibenzo-18-crown-6 ether) was prepared. Magnetic susceptibility experiments reveal slow relaxation of the magnetisation for 2Dy-5Dy, with open magnetic hysteresis up to 14, 12, 15, and 12 K, respectively (∼14 Oe s-1). Fitting the alternating current magnetic susceptibility data for 2Dy-5Dy gives energy barriers to magnetic relaxation (U eff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy-4Dy join a privileged group of SMMs with U eff values of ∼1000 K and greater with magnetic hysteresis at temperatures >10 K. These structurally similar Dy-components permit systematic correlation of the effects of axial and equatorial ligand fields on single-molecule magnet performance. For 2Dy-4Dy, the Dy-components can be grouped into 2Dy-cation/4Dy and 2Dy-anion/3Dy, where the former have almost linear C[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with short average Dy[double bond, length as m-dash]C distances, and the latter have more bent C[double bond, length as m-dash]Dy[double bond, length as m-dash]C units with longer average Dy[double bond, length as m-dash]C bonds. Both U eff and hysteresis temperature are superior for the former pair compared to the latter pair as predicted, supporting the hypothesis that a more linear axial ligand field with shorter M-L distances produces enhanced SMM properties. Comparison with 5Dy demonstrates unusually clear-cut examples of: (i) weakening the equatorial ligand field results in enhancement of the SMM performance of a monometallic system; (ii) a positive correlation between U eff barrier and axial linearity in structurally comparable systems.

Dataset Information

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

Publications

Determination of the electronic structure of a dinuclear dysprosium single molecule magnet without symmetry idealization.

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