A Dy(III) Fluorescent Single-Molecule Magnet Based on a Rhodamine 6G Ligand

The complexes of lanthanide metals, especially dysprosium, can generally exhibit excellent magnetic properties. By means of modifying ligands, dual functions or even multi-functions can be achieved. Here, we synthesized an eight-coordinate Dy(III) complex 1, [Dy(HL-o)2(MeOH)2](ClO4)3·4.5MeOH, which is single-molecule magnet (SMM), and the introduction of the rhodamine 6G chromophore in the ring-opened ligand HL-o realizes ligand-centered fluorescence in addition to SMM. Magnetic measurements and ab initio calculations indicate that the magnetic relaxation for complex 1 should be due to the Raman relaxation process. Studies on magneto-structural correlationship of the rhodamine salicylaldehyde hydrazone Dy(III) complexes show that the calculated energy of the first Kramers Doublet (EKD1) is basically related to the Ophenoxy-Dy-Ophenoxy bond angle, i.e., the larger Ophenoxy-Dy-Ophenoxy bond angle corresponds to a larger EKD1.

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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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An air stable radical-bridged dysprosium single molecule magnet and its neutral counterpart: redox switching of magnetic relaxation dynamics

Chemical Communications ◽

10.1039/c6cc09824j ◽

2017 ◽

Vol 53 (14) ◽

pp. 2283-2286 ◽

Cited By ~ 50

Author(s):

Brian S. Dolinar ◽

Silvia Gómez-Coca ◽

Dimitris I. Alexandropoulos ◽

Kim R. Dunbar

Keyword(s):

Magnetic Properties ◽

Single Molecule ◽

Quantum Tunneling ◽

Magnetic Relaxation ◽

Thermal Relaxation ◽

Relaxation Dynamics ◽

Single Molecule Magnet ◽

Neutral Compound ◽

Redox Switching ◽

P Addition

Addition of a radical to the bridging tetrazine ligand of a Dy2 complex dramatically alters the magnetic properties. The radical complex undergoes magnetic relaxation via a thermal relaxation pathway, whereas the neutral compound relaxes via quantum tunneling of the magnetization.

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Elongation of magnetic relaxation times in a single-molecule magnet through intermetallic interactions: a clamshell-type dinuclear terbium(iii)-phthalocynaninato quadruple-decker complex

Chemical Communications ◽

10.1039/c7cc03553e ◽

2017 ◽

Vol 53 (61) ◽

pp. 8561-8564 ◽

Cited By ~ 22

Author(s):

Yoji Horii ◽

Keiichi Katoh ◽

Brian K. Breedlove ◽

Masahiro Yamashita

Keyword(s):

Relaxation Time ◽

Single Molecule ◽

Magnetic Relaxation ◽

Magnetic Measurements ◽

Relaxation Times ◽

Single Molecule Magnet

Clamshell-type terbium(iii)-phthalocyaninato quadruple-decker complex was synthesized. Magnetic measurements revealed that Tb–Tb interactions caused an increase in the magnetic relaxation time.

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Field-Induced Single-Molecule Magnets of Dysprosium Involving Quinone Derivatives

Magnetochemistry ◽

10.3390/magnetochemistry7020024 ◽

2021 ◽

Vol 7 (2) ◽

pp. 24

Author(s):

Konstantin Martyanov ◽

Jessica Flores Gonzalez ◽

Sergey Norkov ◽

Bertrand Lefeuvre ◽

Vincent Dorcet ◽

...

Keyword(s):

Hydrogen Bonds ◽

Single Molecule ◽

Magnetic Relaxation ◽

Magnetic Measurements ◽

Single Molecule Magnets ◽

Single Molecule Magnet ◽

X Ray ◽

Tert Butyl ◽

Raman Process ◽

Coordination Reaction

The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the two quinone-based derivatives 4,7-di-tert-butyl-2-(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)benzo[d][1,3]dithiole-5,6-dione (L1) and 7,8-dithiabicyclo[4.2.0]octa-1,5-diene-3,4-dione,2,5bis(1,1-dimethylethyl) (L2) led respectively to the complexes [Dy(hfac)3(H2O)(L1)] (1) and [Dy(hfac)3(H2O) (L2)]⋅(C6H14)(CH2Cl2) (2)⋅(C6H14)(CH2Cl2). X-ray structures on single crystal of 1 and 2⋅(C6H14)(CH2Cl2) revealed the coordination of the DyIII on the bischelating oxygenated quinone site and the formation of dimeric species through hydrogen bonds. Ac magnetic measurements highlighted field-induced single-molecule magnet behavior with magnetic relaxation through a Raman process.

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Phenalenyl-based mononuclear dysprosium complexes

Beilstein Journal of Nanotechnology ◽

10.3762/bjnano.7.92 ◽

2016 ◽

Vol 7 ◽

pp. 995-1009 ◽

Cited By ~ 3

Author(s):

Yanhua Lan ◽

Andrea Magri ◽

Olaf Fuhr ◽

Mario Ruben

Keyword(s):

Mass Spectrometry ◽

Thermal Stability ◽

Magnetic Properties ◽

Single Molecule ◽

Magnetic Measurements ◽

Single Molecule Magnet ◽

X Ray ◽

H Nmr ◽

Synthetic Strategy ◽

Lanthanides Complexes

The phenalenyl-based dysprosium complexes [Dy(PLN)2(HPLN)Cl(EtOH)] (1), [Dy(PLN)3(HPLN)]·[Dy(PLN)3(EtOH)]·2EtOH (2) and [Dy(PLN)3(H2O)2]·H2O (3), HPLN being 9-hydroxy-1H-phenalen-1-one, have been synthesized. All compounds were fully characterized by means of single crystal X-ray analysis, paramagnetic 1H NMR, MALDI-TOF mass spectrometry, UV–vis spectrophotometry and magnetic measurements. Both static (dc) and dynamic (ac) magnetic properties of these complexes have been investigated, showing slow relaxation of magnetization, indicative of single molecule magnet (SMM) behavior. Attempts to synthesize sublimable phenalenyl-based dysprosium complexes have been made by implementing a synthetic strategy under anhydrous conditions. The sublimed species were characterized and their thermal stability was confirmed. This opens up the possibility to deposit phenalenyl-based lanthanides complexes by sublimation onto surfaces, an important prerequisite for ongoing studies in molecular spintronics.

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Counterintuitive Single-Molecule Magnet Behaviour in Two Polymorphs of One-Dimensional Compounds Involving Chiral BINOL-Derived Bisphosphate Ligands

Magnetochemistry ◽

10.3390/magnetochemistry7110150 ◽

2021 ◽

Vol 7 (11) ◽

pp. 150

Author(s):

Carlo Andrea Mattei ◽

Bertrand Lefeuvre ◽

Vincent Dorcet ◽

Gilles Argouarch ◽

Olivier Cador ◽

...

Keyword(s):

Single Molecule ◽

Magnetic Relaxation ◽

Magnetic Measurements ◽

Solvent Mixture ◽

Zero Field ◽

Coordination Environment ◽

Single Molecule Magnet ◽

One Dimensional ◽

Slow Magnetic Relaxation ◽

Coordination Reaction

The coordination reaction of the [Dy(hfac)3(H2O)2] units (hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate) with the [8′-(Diphenoxylphosphinyl)[1,1′-binaphthalen]-8-yl]diphenoxylphosphine oxide ligand (L) followed by a crystallisation in a 1:3 CH2Cl2:n-hexane solvent mixture led to the isolation of a new polymorph of formula [(Dy(hfac)3((S)-L))3]n (1). The X-ray structure on single crystal of 1 revealed the formation of a mono-dimensional coordination polymer with three crystallographically independent DyIII centres, which crystallised in the polar chiral P21 space group. Ac magnetic measurements highlighted single-molecule magnet behaviour under both zero and 1000 Oe applied magnetic field with magnetic relaxation through quantum tunneling of the magnetisation (QTM, zero field only) and Raman processes. Despite the three crystallographically independent DyIII centres adopting a distorted D4d coordination environment, a single slow magnetic relaxation contribution was observed at a slower rate than its previously studied [(Dy(hfac)3((S)-L))]n (2) polymorph.

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Slow magnetic relaxation in dinuclear dysprosium and holmium phenoxide bridged complexes: a Dy2 single molecule magnet with a high energy barrier

Inorganic Chemistry Frontiers ◽

10.1039/d1qi00152c ◽

2021 ◽

Author(s):

Matilde Fondo ◽

Julio Corredoira-Vázquez ◽

Ana M. Garcia-Deibe ◽

Jesus Sanmartin Matalobos ◽

Silvia Gómez-Coca ◽

...

Keyword(s):

Crystal Structures ◽

Single Molecule ◽

Energy Barrier ◽

Magnetic Relaxation ◽

High Energy ◽

Single Molecule Magnet ◽

High Energy Barrier ◽

Slow Magnetic Relaxation

Dinuclear [M(H3L1,2,4)]2 (M = Dy, Dy2; M = Ho, Ho2) complexes were isolated from an heptadentate aminophenol ligand. The crystal structures of Dy2·2THF, and the pyridine adducts Dy2·2Py and Ho2·2Py,...

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Multifunctional properties of {CuII2LnIII2} systems involving nitrogen-rich nitronyl nitroxide: single-molecule magnet behavior, luminescence, magnetocaloric effects and heat capacity

Dalton Transactions ◽

10.1039/d0dt04344c ◽

2021 ◽

Author(s):

Hongdao Li ◽

Pei Jing ◽

Jiao Lu ◽

Lu Xi ◽

Qi Wang ◽

...

Keyword(s):

Heat Capacity ◽

Magnetic Properties ◽

Single Molecule ◽

Nitroxide Radical ◽

Nitronyl Nitroxide ◽

Nitronyl Nitroxide Radical ◽

Single Molecule Magnet ◽

Luminescence Behavior ◽

Multifunctional Properties

A family of 3d–4f heterometallic ring-shaped clusters on the basis of a nitrogen-rich nitronyl nitroxide radical have been obtained, and they feature polyfunctionality including magnetic properties, thermodynamics and luminescence behavior.

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