Bis-cyclooctatetraenyl Thulium(II): Highly Reducing Lanthanide Sandwich Single Molecule Magnets

Divalent lanthanide organometallics are well known highly reducing compounds usually used for single electron transfer reactivity and small molecule activation. Thus, their very reactive nature prevented for many years the study of their physical properties, such as magnetic studies on a reliable basis. In this article, the access to rare organometallic sandwich compounds of TmII with the cyclooctatetraenyl (Cot) ligand impacts on the use of divalent organolanthanide compounds as an additional strategy for the design of performing Single Molecule Magnets (SMM). Herein, the first divalent thulium sandwich complex with f13 configuration behaving as a Single Molecule Magnet in absence of DC field is highlighted.

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Simple Method and Materials to Target Co(II)-Dy(III) Multi-Nuclear Magnetic Compounds and Single Molecule Magnets (SMMs): Synthesis, Structure, and Magnetic Studies

Australian Journal of Chemistry ◽

10.1071/ch12336 ◽

2013 ◽

Vol 66 (1) ◽

pp. 75 ◽

Cited By ~ 14

Author(s):

Yan Zhu ◽

Feng Luo ◽

Xue-Feng Feng ◽

Zhen-Wei Liao ◽

Yu-Mei Song ◽

...

Keyword(s):

Single Molecule ◽

Donor Ligands ◽

X Ray Diffraction ◽

Magnetic Studies ◽

Single Molecule Magnets ◽

Simple Method ◽

Single Molecule Magnet ◽

X Ray ◽

Nitrobenzoic Acid ◽

Slow Magnetic Relaxation

In this work, based on mixed N-, O-donor ligands, a series of Co(ii)-Dy(iii) compounds are synthesised and characterised by single crystal X-ray diffraction and magnetic studies. These compounds include Co2(phen)2Dy(PhCOO)7 (1), Co2(phen)2Dy2(PhCOO)10 (2), Co(bpy)Dy(H2O)(CH3-PhCOO)5 (3), Co(phen)Dy(H2O)(CH3-PhCOO)5 (4), Co2(phen)2Dy(NO2-PhCOO)7 (5), Co2(phen)2Dy2(NO2-PhCOO)10 (6), and Co2(bpy)2Dy2(NO2-PhCOO)10 (7), where phen, bpy, CH3-PhCOOH, and NO2-PhCOOH are 1,10-phenanthroline, 2,2′-bipyridine, 3-methylbenzoic acid, and 3-nitrobenzoic acid, respectively. In these cases, di-, tri-, and tetranuclear Co-Dy clusters are observed. Direct current (DC) magnetic susceptibility reveals ferromagnetic or antiferromagnetic behaviour, whilst dynamic magnetic studies disclose single molecule magnet (SMM)-like slow magnetic relaxation for most of these compounds.

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Carboxylate-Bridged Dinuclear Dy2 Single-Molecule Magnets: Synthesis, Structure, and Magnetic Studies

Australian Journal of Chemistry ◽

10.1071/ch12377 ◽

2013 ◽

Vol 66 (1) ◽

pp. 98 ◽

Cited By ~ 6

Author(s):

Yu-mei Song ◽

Feng Luo ◽

Yan Zhu ◽

Xiao-zhao Tian ◽

Gong-ming Sun

Keyword(s):

Magnetic Properties ◽

Single Molecule ◽

Coordination Geometry ◽

Magnetic Studies ◽

Single Molecule Magnets ◽

Chlorobenzoic Acid ◽

Ferromagnetic Interaction ◽

Single Molecule Magnet ◽

The Difference

In this work, the synthesis, structure, and magnetic studies of three dinuclear Dy2 compounds, namely Dy2(bpy)2(L)6 (1), Dy2(phen)2(L)6 (2), Dy2(μ-H2O)2(bpy)2(L)6 (3) are reported in detail, where HL, phen, and bpy are 4-chlorobenzoic acid, 1,10-phenanthroline, and 2,2′-bipyridine. Magnetic studies reveal the intramolecular ferromagnetic interaction and single-molecule magnetic properties of these compounds. The fine-tuned single-molecule magnet properties of compounds 1–3, mainly due to the difference of the coordination geometry of DyIII ions, are highlighted.

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Exchange-Biasing in a Dinuclear Dysprosium(III) Single-Molecule Magnet with a Large Energy Barrier for Magnetization Reversal

10.26434/chemrxiv.10260494 ◽

2019 ◽

Author(s):

Tian Han ◽

Marcus J. Giansiracusa ◽

Zi-Han Li ◽

You-Song Ding ◽

Nicholas F. Chilton ◽

...

Keyword(s):

Single Molecule ◽

Magnetization Reversal ◽

Energy Barrier ◽

Magnetic Hysteresis ◽

Large Energy ◽

Magnetic Studies ◽

Bridging Ligands ◽

Single Molecule Magnet ◽

Exchange Biasing

A dichlorido-bridged dinuclear dysprosium(III) single-molecule magnet [Dy2L2(µ-Cl)2(THF)2] has been made using a diamine-bis(phenolate) ligand, H2L. Magnetic studies show an energy barrier for magnetization reversal (Ueff) around 1000 K. Exchange-biasing effect is clearly seen in magnetic hysteresis with steps up to 4 K. Ab initio calculations exclude the possibility of pure dipolar origin of this effect leading to the conclusion that super-exchange via the chloride bridging ligands is important.

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Correlating Blocking Temperatures in Single Molecule Magnets with Raman Relaxation

10.26434/chemrxiv.7067669 ◽

2018 ◽

Author(s):

Marcus J. Giansiracusa ◽

Andreas Kostopoulos ◽

George F. S. Whitehead ◽

David Collison ◽

Floriana Tuna ◽

...

Keyword(s):

Relaxation Time ◽

Single Molecule ◽

Energy Barrier ◽

Thermal Relaxation ◽

Relaxation Mechanism ◽

Blocking Temperature ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

Key Parameter

We report a six coordinate DyIII single-molecule magnet (SMM) with an energy barrier of 1110 K for thermal relaxation of magnetization. The sample shows no retention of magnetization even at 2 K and this led us to find a good correlation between the blocking temperature and the Raman relaxation regime for SMMs. The key parameter is the relaxation time (𝜏switch) at the point where the Raman relaxation mechanism becomes more important than Orbach.

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Recent advances in lanthanide coordination polymers and clusters with magnetocaloric effect or single-molecule magnet behavior

Dalton Transactions ◽

10.1039/d1dt02797b ◽

2021 ◽

Author(s):

Jun-Jie Hu ◽

Yan Peng ◽

Sui-Jun Liu ◽

He-Rui Wen

Keyword(s):

Quantum Computing ◽

Low Temperature ◽

Magnetocaloric Effect ◽

Coordination Polymers ◽

Single Molecule ◽

Information Storage ◽

Lanthanide Ions ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

Lanthanide Coordination Polymers

The molecular magnetorefrigerant materials for low-temperature magnetic refrigeration and single-molecule magnets for high-density information storage and quantum computing have received extensive attention from chemists and magnetic experts. Lanthanide ions with...

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Polyoxometalate-Supported Lanthanoid Single-Molecule Magnets

Australian Journal of Chemistry ◽

10.1071/ch14166 ◽

2014 ◽

Vol 67 (11) ◽

pp. 1542 ◽

Cited By ~ 24

Author(s):

Michele Vonci ◽

Colette Boskovic

Keyword(s):

Single Molecule ◽

Energy Barrier ◽

Magnetic Relaxation ◽

Donor Ligands ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

Coordination Numbers ◽

Oxygen Donor ◽

Slow Magnetic Relaxation

Polyoxometalates are robust and versatile multidentate oxygen-donor ligands, eminently suitable for coordination to trivalent lanthanoid ions. To date, 10 very different structural families of such complexes have been found to exhibit slow magnetic relaxation due to single-molecule magnet (SMM) behaviour associated with the lanthanoid ions. These families encompass complexes with between one and four of the later lanthanoid ions: Tb, Dy, Ho, Er, and Yb. The lanthanoid coordination numbers vary between six and eleven and a range of coordination geometries are evident. The highest energy barrier to magnetisation reversal measured to date for a lanthanoid–polyoxometalate SMM is Ueff/kB = 73 K for the heterodinuclear Dy–Eu compound (Bu4N)8H4[DyEu(OH)2(γ-SiW10O36)2].

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Structures, fluorescence properties and magnetic properties of a series of rhombus-shaped LnIII4 clusters: magnetocaloric effect and single-molecule-magnet behavior

New Journal of Chemistry ◽

10.1039/c9nj02872b ◽

2019 ◽

Vol 43 (33) ◽

pp. 12941-12949 ◽

Cited By ~ 19

Author(s):

Wen-Min Wang ◽

Li Zhang ◽

Xian-Zhen Li ◽

Li-Yuan He ◽

Xin-Xin Wang ◽

...

Keyword(s):

Magnetic Properties ◽

Magnetocaloric Effect ◽

Single Molecule ◽

Magnetic Relaxation ◽

Magnetic Refrigeration ◽

Fluorescence Properties ◽

Relaxation Processes ◽

Magnetic Studies ◽

Single Molecule Magnet ◽

Slow Magnetic Relaxation

A family LnIII4 clusters were successfully synthesized and structurally characterized. Magnetic studies show that Gd4 cluster displays magnetic refrigeration, while Dy4 cluster demonstrates two distinct slow magnetic relaxation processes.

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Single-molecule magnet properties of a monometallic dysprosium pentalene complex

Chemical Communications ◽

10.1039/c8cc03516d ◽

2018 ◽

Vol 54 (51) ◽

pp. 7085-7088 ◽

Cited By ~ 21

Author(s):

Alexander F. R. Kilpatrick ◽

Fu-Sheng Guo ◽

Benjamin M. Day ◽

Akseli Mansikkamäki ◽

Richard A. Layfield ◽

...

Keyword(s):

Single Molecule ◽

Energy Barriers ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

Dysprosium Complex

The pentalene-ligated dysprosium complex [(η8-Pn†)Dy(Cp*)] (1Dy) (Pn† = [1,4-(iPr3Si)2C8H4]2−) and its magnetically dilute analogue are single-molecule magnets, with energy barriers of 245 cm−1.

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