Single-molecule magnet properties of a monometallic dysprosium pentalene complex

Kilpatrick, Alexander F. R.; Guo, Fu‐Sheng; Day, Benjamin M.; Mansikkamäki, Akseli; Layfield, Richard A.; Cloke, F. Geoffrey N.

doi:10.1039/c8cc03516d

Cited by 37 publications

(17 citation statements)

References 40 publications

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“…Since progress in studies of SMMs is generally experiment-led, synthetic coordination chemistry will continue to play a vital role in advancing our understanding of these fascinating materials. Ligand design is therefore critical, 43 and although varying simple properties, such as the substituents, will account for some progress, there is a strong argument for devising original chemistry. Here, one can imagine multi-decker cyclopentadienyl-dysprosium sandwich complexes possessing interesting properties, in addition to ligands rarely used in lanthanide chemistry, such as cyclobutadienyl and cyclononatetraenyl.…”

Section: Outlook: To Liquid Nitrogen Temperatures and Beyond?mentioning

confidence: 99%

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

2018

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The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization ( U), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {CpDy} display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows U and the magnetic blocking temperature ( T) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.

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Section: Outlook: To Liquid Nitrogen Temperatures and Beyond?mentioning

confidence: 99%

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

2018

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“…Cyclopentadienyl (Cp) and its derivatives have been widely studied as versatile π ligands in rare-earth chemistry . Other π carbocyclic ligands such as cyclobutadienyl, cycloheptatrienyl, dianionic cyclooctatetraene (COT), and pentalene have also been employed. A few heterocyclic ligands have also been employed for the preparation of rare-earth complexes, including boratabenzene and phospholyl ligands, which have been explored as catalysts for olefin polymerization as well as SMMs .…”

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confidence: 99%

Synthesis, Structure, and Magnetic Properties of Rare-Earth Benzoborole Complexes

et al. 2021

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The first examples of benzoborole rare-earth ate complexes [BoRE(COT)][Li(DME)3] (3RE; Bo = benzoborole dianion; COT = cyclooctatetraene; RE = Y, Dy, Er; DME = 1,2-dimethoxyethane) with a sandwich structure have been synthesized by the reaction of a benzoborole dianion with RECl3 followed by treatment with cyclooctatetraene dipotassium salt. These complexes have been fully characterized by X-ray diffraction analysis and IR, UV–vis, and NMR spectroscopy. Remarkably, the Dy and Er complexes exhibit single-molecule-magnet behaviors with effective energy barriers (U eff) of 98 cm–1 (141 K) and 109 cm–1 (157 K), respectively, and their magnetic hysteresis loops were observed at 2 K.

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“…[ 7‐8 ] The first electron delocalized organometallic SMM is (Cp*)Er(COT) reported in 2011. [ 9 ] From then on, the SMMs based on cyclopentadienyl (Cp – ) [ 10 ] and other related cyclic ligands were explored, such as [C 7 H 7 ] 3– , [ 11 ] [C 8 H 8 ] 2– , [ 12 ] [C 9 H 9 ] – , [ 13 ] [C 8 H 6 ] 2– , [ 14 ] [C 4 P] – , [ 15 ] and [C 2 B 9 H 11 ] 2– , [ 16 ] etc ., so as to achieve high performance SMMs. However, some of them such as [C 8 H 8 ] 2– and [C 9 H 9 ] – and some inorganic chelating ligands, [ 17 ] cannot impose the suitable crystal field on Dy 3+ because the larger coordination area.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Chelating Guanidinates for Dysprosium(III) Single‐Molecule Magnets^†

Jin

Zhai

et al. 2021

Chin. J. Chem.

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Guanidinate ligand | Magnetic properties | Lanthanides | Single-molecule magnets | Ab initio calculations Two chelating guanidinate-based dysprosium(III) complexes, namely the monomeric {(Me 3 Si) 2 NC(N i Pr) 2 } 2 Dy(μ-Cl) 2 Li(THF) 2 1 and the dimeric [{(Me 3 Si) 2 NC(N iPr) 2 } 2 Dy(μ-Cl)] 2 2, have been confirmed to be single-molecule magnets. Moreover, the alteration from 1 to 2 leads to an obvious mitigated quantum tunnelling of magnetization at zero field of the hysteresis loop and much enhanced magnetic relaxation barrier (up to 312 K). 5% dilution with the yttrium(III) analogue for 2 shows no clear change for the hysteresis, indicating the single-ion nature of the magnetic behavior.

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Single-molecule magnet properties of a monometallic dysprosium pentalene complex

Cited by 37 publications

References 40 publications

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

Synthesis, Structure, and Magnetic Properties of Rare-Earth Benzoborole Complexes

Chelating Guanidinates for Dysprosium(III) Single‐Molecule Magnets^†

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Single-molecule magnet properties of a monometallic dysprosium pentalene complex

Cited by 37 publications

References 40 publications

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

Synthesis, Structure, and Magnetic Properties of Rare-Earth Benzoborole Complexes

Chelating Guanidinates for Dysprosium(III) Single‐Molecule Magnets†

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Product

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Chelating Guanidinates for Dysprosium(III) Single‐Molecule Magnets^†