Insight into D6h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single-Ion Magnets

Three dysprosium(III) single-molecule magnets (SMMs) with the rare hexagonal bipyramidal geometry have been isolated for the first time. Following a novel synthetic strategy where the strong uniaxial ligand field generated by the Ph3SiO- (Ph3SiO- = anion of triphenylsilanol) and the 2,4-di-tBu-PhO- (2,4-di-tBu-PhO- = anion of 2,4-di-tertbutylphenol) ligands combined with the weak equatorial field of the ligand LN6, leads to [DyIII(LN6)(2,4-di-tBu-PhO)2](PF6) (1), [DyIII(LN6)(Ph3SiO)2](PF6) (2) and [DyIII(LN6)(Ph3SiO)2](BPh4) (3) hexagonal bipyramidal complexes with high anisotropy barriers of Ueff = 973 K for 1, Ueff = 1080 K for 2 and Ueff = 1124 K for 3 under zero applied dc field. Ab initio calculations predict that the dominant magnetization reversal barrier of these complexes expands up to the 3rd Kramers doublet, thus revealing for the first time the exceptional uniaxial magnetic anisotropy that even the six equatorial donor atoms fail to negate, opening up the possibility to other higher-order symmetry SMMs.

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Ligand-Field Energy Splitting in Lanthanide-Based Single-Molecule Magnets by NMR Spectroscopy

Inorganic Chemistry ◽

10.1021/acs.inorgchem.7b02704 ◽

2017 ◽

Vol 56 (24) ◽

pp. 15285-15294 ◽

Cited By ~ 12

Author(s):

Markus Hiller ◽

Saskia Krieg ◽

Naoto Ishikawa ◽

Markus Enders

Keyword(s):

Nmr Spectroscopy ◽

Single Molecule ◽

Field Energy ◽

Ligand Field ◽

Energy Splitting ◽

Single Molecule Magnets

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Magneto-Structural Correlations in a Series of Pseudotetrahedral [CoII(XR)4]2– Single Molecule Magnets: An ab Initio Ligand Field Study

Inorganic Chemistry ◽

10.1021/acs.inorgchem.5b01706 ◽

2015 ◽

Vol 54 (20) ◽

pp. 9948-9961 ◽

Cited By ~ 69

Author(s):

Elizaveta A. Suturina ◽

Dimitrios Maganas ◽

Eckhard Bill ◽

Mihail Atanasov ◽

Frank Neese

Keyword(s):

Ab Initio ◽

Field Study ◽

Single Molecule ◽

Ligand Field ◽

Single Molecule Magnets

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3d single-ion magnets

Chemical Society Reviews ◽

10.1039/c4cs00439f ◽

2015 ◽

Vol 44 (8) ◽

pp. 2135-2147 ◽

Cited By ~ 456

Author(s):

Gavin A. Craig ◽

Mark Murrie

Keyword(s):

Magnetic Properties ◽

Transition Metal ◽

Single Molecule ◽

Metal Ion ◽

Ligand Field ◽

Single Molecule Magnets ◽

Transition Metal Ion ◽

Recent Approach

This review describes the recent approach to obtain single-molecule magnets where the magnetic properties arise from just one first row transition metal ion in a suitable ligand field.

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Toward heterometallic single-molecule magnets: Synthetic strategy, structures and properties of 3d–4f discrete complexes

Coordination Chemistry Reviews ◽

10.1016/j.ccr.2014.10.004 ◽

2015 ◽

Vol 289-290 ◽

pp. 74-122 ◽

Cited By ~ 315

Author(s):

Ke Liu ◽

Wei Shi ◽

Peng Cheng

Keyword(s):

Single Molecule ◽

Single Molecule Magnets ◽

Synthetic Strategy ◽

Structures And Properties

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Deciphering the Role of Symmetry and Ligand Field in Designing Three-Coordinate Uranium and Plutonium Single-Molecule Magnets

Inorganic Chemistry ◽

10.1021/acs.inorgchem.1c02646 ◽

2022 ◽

Author(s):

Sourav Dey ◽

Gopalan Rajaraman

Keyword(s):

Single Molecule ◽

Ligand Field ◽

Single Molecule Magnets

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A ligand-field study of the ground spin-state magnetic anisotropy in a family of hexanuclear Mn(iii) single-molecule magnets

Dalton Transactions ◽

10.1039/b718225b ◽

2008 ◽

pp. 2277 ◽

Cited By ~ 26

Author(s):

Stergios Piligkos ◽

Jesper Bendix ◽

Høgni Weihe ◽

Constantinos J. Milios ◽

Euan K. Brechin

Keyword(s):

Magnetic Anisotropy ◽

Field Study ◽

Spin State ◽

Single Molecule ◽

Ligand Field ◽

Single Molecule Magnets ◽

Ground Spin State

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Incorporation of expanded organic cations in dysprosium(III) borohydrides for achieving luminescent molecular nanomagnets

Scientific Reports ◽

10.1038/s41598-021-88446-7 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Wojciech Wegner ◽

Jakub J. Zakrzewski ◽

Mikolaj Zychowicz ◽

Szymon Chorazy

Keyword(s):

Magnetic Anisotropy ◽

Single Molecule ◽

Unit Cell ◽

Organic Cations ◽

Single Molecule Magnets ◽

Higher Symmetry ◽

Magnetic Switching ◽

Unit Cells ◽

Slow Magnetic Relaxation ◽

Insight Into

AbstractLuminescent single-molecule magnets (SMMs) constitute a class of molecular materials offering optical insight into magnetic anisotropy, magnetic switching of emission, and magnetic luminescent thermometry. They are accessible using lanthanide(III) complexes with advanced organic ligands or metalloligands. We present a simple route to luminescent SMMs realized by the insertion of well-known organic cations, tetrabutylammonium and tetraphenylphosphonium, into dysprosium(III) borohydrides, the representatives of metal borohydrides investigated due to their hydrogen storage properties. We report two novel compounds, [n-Bu4N][DyIII(BH4)4] (1) and [Ph4P][DyIII(BH4)4] (2), involving DyIII centers surrounded by four pseudo-tetrahedrally arranged BH4– ions. While 2 has higher symmetry and adopts a tetragonal unit cell (I41/a), 1 crystallizes in a less symmetric monoclinic unit cell (P21/c). They exhibit yellow room-temperature photoluminescence related to the f–f electronic transitions. Moreover, they reveal DyIII-centered magnetic anisotropy generated by the distorted arrangement of four borohydride anions. It leads to field-induced slow magnetic relaxation, well-observed for the magnetically diluted samples, [n-Bu4N][YIII0.9DyIII0.1(BH4)4] (1@Y) and [Ph4P][YIII0.9DyIII0.1(BH4)4] (2@Y). 1@Y exhibits an Orbach-type relaxation with an energy barrier of 26.4(5) K while only the onset of SMM features was found in 2@Y. The more pronounced single-ion anisotropy of DyIII complexes of 1 was confirmed by the results of the ab initio calculations performed for both 1–2 and the highly symmetrical inorganic DyIII borohydrides, α/β-Dy(BH4)3, 3 and 4. The magneto-luminescent character was achieved by the implementation of large organic cations that lower the symmetry of DyIII centers inducing single-ion anisotropy and separate them in the crystal lattice enabling the emission property. These findings are supported by the comparison with 3 and 4, crystalizing in cubic unit cells, which are not emissive and do not exhibit SMM behavior.

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Efficient enhancement of magnetic anisotropy by optimizing the ligand-field in a typically tetranuclear dysprosium cluster

Dalton Transactions ◽

10.1039/c5dt00880h ◽

2015 ◽

Vol 44 (17) ◽

pp. 8150-8155 ◽

Cited By ~ 24

Author(s):

Jiang Liu ◽

Yan-Cong Chen ◽

Zhong-Xia Jiang ◽

Jun-Liang Liu ◽

Jian-Hua Jia ◽

...

Keyword(s):

Magnetic Field ◽

External Magnetic Field ◽

Magnetic Anisotropy ◽

Single Molecule ◽

Thermal Energy ◽

Ligand Field ◽

Energy Barriers ◽

Single Molecule Magnets ◽

Applied External Magnetic Field

Two tetranuclear dysprosium single molecule magnets under a zero applied external magnetic field showing high thermal energy barriers which are among the highest within the reported tetranuclear lanthanide-based SMMs.

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Boosting axiality in stable high-coordinate Dy(iii) single-molecule magnets

Chemical Communications ◽

10.1039/c9cc00965e ◽

2019 ◽

Vol 55 (42) ◽

pp. 5950-5953 ◽

Cited By ~ 16

Author(s):

Angelos B. Canaj ◽

Mukesh Kumar Singh ◽

Emma Regincós Marti ◽

Marko Damjanović ◽

Claire Wilson ◽

...

Keyword(s):

Single Molecule ◽

Computational Study ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

Insight Into

A combined synthetic, structural, magnetic and computational study gives insight into improving the single-molecule magnet behaviour of stable high-coordinate Dy(iii) complexes.

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