Search results for "Single-Molecule Magnets"
showing 10 items of 16 documents
Exploring the Slow Relaxation of the Magnetization in CoIII -Decorated {DyIII 2 } Units
2016
We have prepared and structurally characterized a new member of the butterfly-like {CoIII 2DyIII 2} single-molecule magnets (SMMs) through further CoIIIdecoration, with the formula [CoIII 4DyIII 2(OH)2(teaH)2(tea)2(Piv)6] (teaH3=triethanolamine; Piv=trimethylacetate or pivalate). Direct current (DC) susceptibility and magnetization measurements were performed allowing the extraction of possible crystal-field parameters. A simple electrostatic modeling shows reasonable agreement with experimental data. Alternating current (AC) susceptibility measurements under a zero DC field and under small applied fields were performed at different frequencies (i.e., 10–1500 Hz) and at low temperatures (i.…
Ferromagnetic coupled μ-phenoxo-μ-carboxylato heterodinuclear complexes based on the Cr(salen) moiety: Structural and magnetic characterization
2009
The synthesis, crystal structure, and magneto-chemical characterization of two new unprecedented μ-phenoxo-μ-carboxylato heterodinuclear complexes based on the Cr(salen) moiety (salen = N,N′-bis(salicylidene)ethylenediamine), [MII(O2C(CH3)3)(OH2)2(μ-O2C(CH3)3)(μ-salen)CrIII(O2C(CH3)3)], M = Ni (2), Co(3) are reported. The dinuclear complexes were obtained starting from the mononuclear trans-[Cr(salen)(CN)2]PPh4 (1), whose crystal structure is also reported. They show a trans arrangement of the Cr(salen) unit, bridging through the phenolate O atoms to a second metal center. An additional μ2-O2-carboxylato bridge and a further monodentating carboxylate ligand complete the roughly octahedral C…
Dynamic Magnetic and Optical Insight into a High Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnet
2017
The pentagonal bipyramidal single-ion magnets (SIMs) are among the most attractive prototypes of high-performance single-molecule magnets (SMMs). Here, a fluorescence-active phosphine oxide ligand CyPh2PO (=cyclohexyl(diphenyl)phosphine oxide) was introduced into [Dy(CyPh2PO)2(H2O)5]Br3⋅2 (CyPh2PO)⋅EtOH⋅3 H2O, and combined dynamic magnetic measurement, optical characterization, ab initio calculation, and magneto-optical correlation of this high-performance pseudo-D5h DyIII SIM with large Ueff (508(2) K) and high magnetic hysteresis temperature (19 K) were performed. This work provides a deeper insight into the rational design of promising molecular magnets.
Tailoring the Exchange Interaction in Covalently Linked Basic Carboxylate Clusters through Bridging Ligand Selection
2012
We are reporting new dimeric units of basic carboxylates bearing the {Fe III 2M IIO} motif for M = Co and Ni, covalently bound through the tetradentate bridging (LL) 2,2′-azopyiridine (azpy) and 2,3-di(2-pyridyl)quinoxaline ligands (dpq). We structurally characterized the hexanuclear clusters, and their magnetic properties have been fully analyzed. DFT calculations have been performed as a supplementary tool. All results evidence a weak antiferromagnetic interaction through the bridging ligands between isolated spin ground states arising from intra-Fe 2MO core exchange couplings. Together with the pioneer 2,2′-bipyrimidine bridged systems, the new complexes reported constitute a family of c…
Carbonyl Back-Bonding Influencing the Rate of Quantum Tunnelling in a Dysprosium Metallocene Single-Molecule Magnet.
2019
The isocarbonyl-ligated metallocene coordination polymers [Cp*2M(μ-OC)W(Cp)(CO)(μ-CO)]∞ were synthesized with M = Gd (1, L = THF) and Dy (2, no L). In a zero direct-current field, the dysprosium version 2 was found to be a single-molecule magnet (SMM), with analysis of the dynamic magnetic susceptibility data revealing that the axial metallocene coordination environment leads to a large anisotropy barrier of 557(18) cm–1 and a fast quantum-tunnelling rate of ∼3.7 ms. Theoretical analysis of two truncated versions of 2, [Cp*2Dy{(μ-OC)W(Cp)(CO)2}2]− (2a), and [Cp*2Dy(OC)2]+ (2b), in which the effects of electron correlation outside the 4f orbital space were studied, revealed that tungsten-to-…
A Dysprosium Metallocene Single-Molecule Magnet Functioning at the Axial Limit
2017
Abstraction of a chloride ligand from the dysprosium metallocene [(Cpttt)2DyCl] (1Dy Cpttt=1,2,4‐tri(tert‐butyl)cyclopentadienide) by the triethylsilylium cation produces the first base‐free rare‐earth metallocenium cation [(Cpttt)2Dy]+ (2Dy) as a salt of the non‐coordinating [B(C6F5)4]− anion. Magnetic measurements reveal that [2Dy][B(C6F5)4] is an SMM with a record anisotropy barrier up to 1277 cm−1 (1837 K) in zero field and a record magnetic blocking temperature of 60 K, including hysteresis with coercivity. The exceptional magnetic axiality of 2Dy is further highlighted by computational studies, which reveal this system to be the first lanthanide SMM in which all low‐lying Kramers doub…
A [Cr2Ni] coordination polymer: slow relaxation of magnetization in quasi-one-dimensional ferromagnetic chains
2018
The reaction of [Cr3IIIO(OAc)6(H2O)3]NO3·AcOH with 2-hydroxynaphthaldehyde, 2-amino-isobutyric acid and NiCl2·6H2O in MeOH, under basic and solvothermal conditions, led to the formation of the quasi-1D coordination polymer {[CrIII2NiII(L)4(MeOH)2]}n (where L = the dianion of the Schiff base between 2-hydroxynaphthaldehyde and 2-amino-isobutyric acid), which behaves as a ferromagnetic chain, displaying slow relaxation of magnetization.
A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Dev…
2019
The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2′-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow …
Structural and magnetic characterization of a 1D chain of [Co(II)2(mu-aqua)(mu-carboxylate)2] strung cores.
2009
A novel 1D chain built up from stringing of [Co2(μ-OH 2)(μ-O2CC(CH3)3)2] units with the bridging 2,2′-bipyrimidine ligand has been synthesized and structurally characterized. The chains are well isolated from each other by the bulky tert-butyl groups of the carboxlyates and show an alternating zigzag configuration for the Co(II) metallic centres. DC magnetic measurements show anti-ferromagnetic coupling, Jca.-3 cm-1 between adjacent Co(II) ions along the chain. Noticeably, good data fitting was obtained by means of simple models that neglect any kind of first order orbital contribution to the spin ground state, which is normally observed in Co(II) complexes. These results were further confi…
Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet
2018
Breaking through the nitrogen ceiling Single-molecule magnets could prove useful in miniaturizing a wide variety of devices. However, their application has been severely hindered by the need to cool them to extremely low temperature using liquid helium. Guo et al. now report a dysprosium compound that manifests magnetic hysteresis at temperatures up to 80 kelvin. The principles applied to tuning the ligands in this complex could point the way toward future architectures with even higher temperature performance. Science , this issue p. 1400