Relaxation dynamics of dysprosium(iii) single molecule magnets

2011 ◽  
Vol 40 (39) ◽  
pp. 9953 ◽  
Author(s):  
Yun-Nan Guo ◽  
Gong-Feng Xu ◽  
Yang Guo ◽  
Jinkui Tang
Keyword(s):  
Single Molecule ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets

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

2021 ◽  
Author(s):  
Daniel Reta ◽  
Jon G. C. Kragskow ◽  
Nicholas Chilton
Keyword(s):  
High Temperature ◽  
Ab Initio ◽  
Single Molecule ◽  
Magnetic Relaxation ◽  
Quantitative Prediction ◽  
Relaxation Dynamics ◽  
Efficient Design ◽  
Relaxation Rates ◽  
Design Strategies ◽  
Single Molecule Magnets

<p>Organometallic molecules based on [Dy(Cp<sup>R</sup>)<sub>2</sub>]<sup>+</sup> cations have emerged as clear front-runners in the search for high-temperature single-molecule magnets. However, despite a growing family of structurally-similar molecules, these molecules show significant variations in their magnetic properties, demonstrating the importance of understanding magneto-structural relationships towards developing more efficient design strategies. Here we refine our <i>ab initio</i> spin dynamics methodology and show that it is capable of quantitative prediction of relative relaxation rates in the Orbach region. Applying it to all reported [Dy(Cp<sup>R</sup>)<sub>2</sub>]<sup>+</sup> cations allows us to tease out differences in their relaxation dynamics, highlighting that the main discriminant is the magnitude of the crystal field splitting. We subsequently employ the method to predict relaxation rates for a series of hypothetical organometallic sandwich compounds, revealing an upper limit to the effective barrier to magnetic relaxation of around 2200 K, which has been reached. However, we show that further improvements to single-molecule magnets can be made by moving vibrational modes off-resonance with electronic excitations.</p>

scholarly journals Probing Relaxation Dynamics in Five‐Coordinate Dysprosium Single‐Molecule Magnets

2020 ◽  
Vol 26 (35) ◽  
pp. 7774-7778 ◽  
Author(s):  
Vijay S. Parmar ◽  
Fabrizio Ortu ◽  
Xiaozhou Ma ◽  
Nicholas F. Chilton ◽  
Rodolphe Clérac ◽  
...  
Keyword(s):  
Single Molecule ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets

See-Saw Shaped Dy(III) Single-Molecule Magnets with High Anisotropy Barriers

2020 ◽  
Author(s):  
Katie L. M. Harriman ◽  
Jesse Murillo ◽  
Elizaveta A. Suturina ◽  
Skye Fortier ◽  
Muralee Murugesu
Keyword(s):  
Magnetic Susceptibility ◽  
Single Molecule ◽  
Molecular Geometry ◽  
High Energy ◽  
Zero Field ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets ◽  
Ancillary Ligands ◽  
Spin Reversal ◽  
Magnetic Spin

<p>Utilizing a terphenyl bisanilide ligand, two Dy(III) complexes [K(DME)<sub>x</sub>][L<sup>Ar</sup>Dy(X)<sub>2</sub>] (L<sup>Ar</sup> = {C<sub>6</sub>H<sub>4</sub>[(2,6-<i><sup>i</sup></i>PrC<sub>6</sub>H<sub>3</sub>)NC<sub>6</sub>H<sub>4</sub>]<sub>2</sub>}<sup>2-</sup>), X = Cl (<b>1</b>) and X = I (<b>2</b>) were synthesized. The ligand imposes an unusual see-saw shaped molecular geometry leading to a coordinatively unsaturated complex with near-linear N-Dy-N (avg. 159.9° for<b>1</b> and avg. 160.3<sup>o</sup> for <b>2</b>) bond angles. These complexes exhibit Single-Molecule Magnet (SMM) behavior with significant uniaxial magnetic anisotropy as a result of the transverse coordination of the bisanlide ligand which yields high energy barriers to magnetic spin reversal of <i>U</i><sub>eff</sub> = 1334 K/ 927cm<sup>-1</sup> (<b>1</b>) and 1299 K/ 903 cm<sup>-1</sup> (<b>2</b>) in zero field. Magneto-structural correlations are discussed with the goal of finding a link between halide ancillary ligands in the structurally analogous complexes and the through barrier relaxation dynamics observed in the ac magnetic susceptibility, despite the similar dc magnetic susceptibility for compounds <b>1</b> and <b>2</b>. <i>Ab initio</i> calculations reveal that the dominant crystal field of the bisanilide ligand controls the orientation of the main magnetic axis which runs nearly parallel to the N-Dy-N bonds, and defines the height of the energy barrier. Thus, further validating the use of transverse ligands to enhance the SMM properties of Dy(III) ions.</p>

scholarly journals Tetranuclear dysprosium single-molecule magnets: tunable magnetic interactions and magnetization dynamics through modifying coordination number

2019 ◽  
Vol 48 (6) ◽  
pp. 2135-2141 ◽  
Author(s):  
Kun Zhang ◽  
Gao-Peng Li ◽  
Vincent Montigaud ◽  
Olivier Cador ◽  
Boris Le Guennic ◽  
...  
Keyword(s):  
Coordination Number ◽  
Single Molecule ◽  
Magnetic Interactions ◽  
Relaxation Dynamics ◽  
Magnetization Dynamics ◽  
Single Molecule Magnets ◽  
Coordination Environment ◽  
Coordination Sites ◽  
Fine Control

The magnetic interactions and relaxation dynamics are modulated in two polynuclear dysprosium(iii) SMMs through a fine control of the coordination environment on the changeable coordination sites.

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

2021 ◽  
Author(s):  
Daniel Reta ◽  
Jon G. C. Kragskow ◽  
Nicholas Chilton
Keyword(s):  
High Temperature ◽  
Ab Initio ◽  
Single Molecule ◽  
Magnetic Relaxation ◽  
Quantitative Prediction ◽  
Relaxation Dynamics ◽  
Efficient Design ◽  
Relaxation Rates ◽  
Design Strategies ◽  
Single Molecule Magnets

<p>Organometallic molecules based on [Dy(Cp<sup>R</sup>)<sub>2</sub>]<sup>+</sup> cations have emerged as clear front-runners in the search for high-temperature single-molecule magnets. However, despite a growing family of structurally-similar molecules, these molecules show significant variations in their magnetic properties, demonstrating the importance of understanding magneto-structural relationships towards developing more efficient design strategies. Here we refine our <i>ab initio</i> spin dynamics methodology and show that it is capable of quantitative prediction of relative relaxation rates in the Orbach region. Applying it to all reported [Dy(Cp<sup>R</sup>)<sub>2</sub>]<sup>+</sup> cations allows us to tease out differences in their relaxation dynamics, highlighting that the main discriminant is the magnitude of the crystal field splitting. We subsequently employ the method to predict relaxation rates for a series of hypothetical organometallic sandwich compounds, revealing an upper limit to the effective barrier to magnetic relaxation of around 2200 K, which has been reached. However, we show that further improvements to single-molecule magnets can be made by moving vibrational modes off-resonance with electronic excitations.</p>

Relaxation dynamics in see-saw shaped Dy(iii) single-molecule magnets

2020 ◽  
Vol 7 (24) ◽  
pp. 4805-4812 ◽  
Author(s):  
Katie L. M. Harriman ◽  
Jesse Murillo ◽  
Elizaveta A. Suturina ◽  
Skye Fortier ◽  
Muralee Murugesu
Keyword(s):  
Single Molecule ◽  
Zero Field ◽  
Effective Energy ◽  
Relaxation Dynamics ◽  
Energy Barriers ◽  
Single Molecule Magnets

Unusual see-saw shaped Dy(iii) single-molecule magnets, [K(DME)n][LArDy(X)2] (LAr = {C6H4[(2,6-iPrC6H3)NC6H4]2}2−), X = Cl (1) and X = I (2) were synthesized and display high effective energy barriers (Ueff = 1278–1334 K) in zero field.

Linear hexanuclear helical dysprosium single-molecule magnets: the effect of axial substitution on magnetic interactions and relaxation dynamics

2019 ◽  
Vol 48 (37) ◽  
pp. 14062-14068 ◽  
Author(s):  
Jingjing Lu ◽  
Xiao-Lei Li ◽  
Zhenhua Zhu ◽  
Shuting Liu ◽  
Qianqian Yang ◽  
...  
Keyword(s):  
Single Molecule ◽  
Magnetic Relaxation ◽  
Structural Modification ◽  
Relaxation Behavior ◽  
Magnetic Interactions ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets

Structural modification of the Dy6 cores of [Dy6L3(SCN)6(DMF)8]·4DMF (1) and [Dy6L3(NO3)6(DMF)4(H2O)2]·8DMF (2) results in the transition of magnetic relaxation behavior from single relaxation to multiple relaxation.

See-Saw Shaped Dy(III) Single-Molecule Magnets with High Anisotropy Barriers

2020 ◽  
Author(s):  
Katie L. M. Harriman ◽  
Jesse Murillo ◽  
Elizaveta A. Suturina ◽  
Skye Fortier ◽  
Muralee Murugesu
Keyword(s):  
Magnetic Susceptibility ◽  
Single Molecule ◽  
Molecular Geometry ◽  
High Energy ◽  
Zero Field ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets ◽  
Ancillary Ligands ◽  
Spin Reversal ◽  
Magnetic Spin

<p>Utilizing a terphenyl bisanilide ligand, two Dy(III) complexes [K(DME)<sub>x</sub>][L<sup>Ar</sup>Dy(X)<sub>2</sub>] (L<sup>Ar</sup> = {C<sub>6</sub>H<sub>4</sub>[(2,6-<i><sup>i</sup></i>PrC<sub>6</sub>H<sub>3</sub>)NC<sub>6</sub>H<sub>4</sub>]<sub>2</sub>}<sup>2-</sup>), X = Cl (<b>1</b>) and X = I (<b>2</b>) were synthesized. The ligand imposes an unusual see-saw shaped molecular geometry leading to a coordinatively unsaturated complex with near-linear N-Dy-N (avg. 159.9° for<b>1</b> and avg. 160.3<sup>o</sup> for <b>2</b>) bond angles. These complexes exhibit Single-Molecule Magnet (SMM) behavior with significant uniaxial magnetic anisotropy as a result of the transverse coordination of the bisanlide ligand which yields high energy barriers to magnetic spin reversal of <i>U</i><sub>eff</sub> = 1334 K/ 927cm<sup>-1</sup> (<b>1</b>) and 1299 K/ 903 cm<sup>-1</sup> (<b>2</b>) in zero field. Magneto-structural correlations are discussed with the goal of finding a link between halide ancillary ligands in the structurally analogous complexes and the through barrier relaxation dynamics observed in the ac magnetic susceptibility, despite the similar dc magnetic susceptibility for compounds <b>1</b> and <b>2</b>. <i>Ab initio</i> calculations reveal that the dominant crystal field of the bisanilide ligand controls the orientation of the main magnetic axis which runs nearly parallel to the N-Dy-N bonds, and defines the height of the energy barrier. Thus, further validating the use of transverse ligands to enhance the SMM properties of Dy(III) ions.</p>

Counter anions influence the relaxation dynamics of phenoxy-bridged Dy2 single molecule magnets

2020 ◽  
Vol 49 (35) ◽  
pp. 12372-12379 ◽  
Author(s):  
Shuting Liu ◽  
Jingjing Lu ◽  
Xiao-Lei Li ◽  
Zhenhua Zhu ◽  
Jinkui Tang
Keyword(s):  
Relaxation Process ◽  
Single Molecule ◽  
Relaxation Dynamics ◽  
Counter Anion ◽  
Dynamic Relaxation ◽  
Single Molecule Magnets

Structural and magnetic investigations into four dinuclear dysprosium complexes reveal that the counter anion influences the dynamic relaxation process in these complexes.

Tuning the Magnetic Interactions and Relaxation Dynamics of Dy 2 Single‐Molecule Magnets

2015 ◽  
Vol 21 (40) ◽  
pp. 14099-14106 ◽  
Author(s):  
Shufang Xue ◽  
Yun‐Nan Guo ◽  
Liviu Ungur ◽  
Jinkui Tang ◽  
Liviu F. Chibotaru
Keyword(s):  
Single Molecule ◽  
Magnetic Interactions ◽  
Relaxation Dynamics ◽  
Single Molecule Magnets
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