Influence of antisymmetric exchange interaction on quantum tunneling of magnetization in a dimeric molecular magnet Mn6

We present magnetization measurements on the single molecule magnet Mn6, revealing various tunnel transitions inconsistent with a giant-spin description. We propose a dimeric model of the molecule with two coupled spins S=6, which involves crystal-field anisotropy, symmetric Heisenberg exchange interaction, and antisymmetric Dzyaloshinskii-Moriya exchange interaction. We show that this simplified model of the molecule explains the experimentally observed tunnel transitions and that the antisymmetric exchange interaction between the spins gives rise to tunneling processes between spin states belonging to different spin multiplets.Comment: 5 pages, 4 figure

Putting the Squeeze on Molecule-Based Magnets: Exploiting Pressure to Develop Magneto-Structural Correlations in Paramagnetic Coordination Compounds

The cornerstone of molecular magnetism is a detailed understanding of the relationship between structure and magnetic behaviour, i.e., the development of magneto-structural correlations. Traditionally, the synthetic chemist approaches this challenge by making multiple compounds that share a similar magnetic core but differ in peripheral ligation. Changes in the ligand framework induce changes in the bond angles and distances around the metal ions, which are manifested in changes to magnetic susceptibility and magnetisation data. This approach requires the synthesis of a series of different ligands and assumes that the chemical/electronic nature of the ligands and their coordination to the metal, the nature and number of counter ions and how they are positioned in the crystal lattice, and the molecular and crystallographic symmetry have no effect on the measured magnetic properties. In short, the assumption is that everything outwith the magnetic core is inconsequential, which is a huge oversimplification. The ideal scenario would be to have the same complex available in multiple structural conformations, and this is something that can be achieved through the application of external hydrostatic pressure, correlating structural changes observed through high-pressure single crystal X-ray crystallography with changes observed in high-pressure magnetometry, in tandem with high-pressure inelastic neutron scattering (INS), high-pressure electron paramagnetic resonance (EPR) spectroscopy, and high-pressure absorption/emission/Raman spectroscopy. In this review, which summarises our work in this area over the last 15 years, we show that the application of pressure to molecule-based magnets can (reversibly) (1) lead to changes in bond angles, distances, and Jahn–Teller orientations; (2) break and form bonds; (3) induce polymerisation/depolymerisation; (4) enforce multiple phase transitions; (5) instigate piezochromism; (6) change the magnitude and sign of pairwise exchange interactions and magnetic anisotropy, and (7) lead to significant increases in magnetic ordering temperatures

Magnetic exchange, anisotropy and excitonic fluctuations in a [Ni^II₇] Anderson wheel

The solvothermal reaction of Ni(ClO4)2·6H2O with hmpH and picH in a basic MeOH solution affords [Ni7(hmp)7.55(pic)4.45](ClO4)2·6MeOH (1·6MeOH) directly upon cooling the mother liquor. The metallic skeleton of 1 describes a [NiII7] centred hexagon, commonly referred to as an Anderson wheel. Magnetic measurements reveal ferromagnetic exchange between the central Ni ion and the ring Ni ions, and antiferromagnetic exchange between neighbouring ring Ni ions. They also confirm the presence of easy-plane anisotropy for the central Ni ion, and easy-axis anisotropy for the ring Ni ions, in agreement with DFT calculations and neutron scattering. For the analysis of the latter we apply an excitonic formalism using a Green's function response theory.</p

Squaring the cube:a family of octametallic lanthanide complexes including a Dy8 single-molecule magnet

International audienceA series of isostructural octanuclear lanthanide complexes of general formula [Ln(8)(sao)(4)(mu(3)-OH)(4)( NO3)(12)(DMF)(12)] (Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8); DMF = dimethylformamide) have been prepared via reactions of salicylaldoxime (saoH(2)), tetramethylammonium hydroxide (Me4NOH) with the appropriate lanthanide nitrate salt (Ln(NO3)(3)center dot 6H(2)O). The metallic skeletons of the complexes describe [Ln(4)] tetrahedra encapsulated inside a [Ln(4)] square with the inner core stabilised through mu(3)-OH-ions and the periphery by mu(4)-sao(2)-ligands. The magnetic properties of compounds 2-8 were investigated by dc and ac magnetometry. Temperature dependent ac magnetic susceptibility data reveal that the dysprosium analogue (6) displays an out-of-phase signal in the absence of an applied magnetic field indicative of slow relaxation of the magnetization typical of a Single-Molecule Magnet (SMM). Micro-SQUID measurements reveal temperature and sweep rate dependent hysteresis below 1.0 K

An IRAK1-PIN1 signalling axis drives intrinsic tumour resistance to radiation therapy

Drug-based strategies to overcome tumour resistance to radiotherapy (R-RT) remain limited by the single-agent toxicity of traditional radiosensitizers (for example, platinums) and a lack of targeted alternatives. In a screen for compounds that restore radiosensitivity in p53 mutant zebrafish while tolerated in non-irradiated wild-type animals, we identified the benzimidazole anthelmintic oxfendazole. Surprisingly, oxfendazole acts via the inhibition of IRAK1, a kinase thus far implicated in interleukin-1 receptor (IL-1R) and Toll-like receptor (TLR) immune responses. IRAK1 drives R-RT in a pathway involving IRAK4 and TRAF6 but not the IL-1R/TLR-IRAK adaptor MyD88. Rather than stimulating nuclear factor-κB, radiation-activated IRAK1 prevented apoptosis mediated by the PIDDosome complex (comprising PIDD, RAIDD and caspase-2). Countering this pathway with IRAK1 inhibitors suppressed R-RT in tumour models derived from cancers in which TP53 mutations predict R-RT. Moreover, IRAK1 inhibitors synergized with inhibitors of PIN1, a prolyl isomerase essential for IRAK1 activation in response to pathogens and, as shown here, in response to ionizing radiation. These data identify an IRAK1 radiation-response pathway as a rational chemoradiation therapy target

Studies on bifunctional Fe(II)-triazole spin crossover nanoparticles: time-dependent luminescence, surface grafting and the effect of a silica shell and hydrostatic pressure on the magnetic properties

Pure and silica wrapped Fe(II)-triazole (FeHTrz) spin-crossover (SCO) nanoparticles have been prepared following a water-in-oil synthetic procedure. The size and shape can be tuned by controlling the Fe(II) and triazole concentrations in the aqueous phase. The magnetic properties of these nanoparticles are strongly affected by the presence of a silica shell embedding the nanostructured FeHTrz polymer. Whereas bare FeHTrz nanoparticles exhibit abrupt and cooperative spin transition with 24–35K-wide thermal hysteresis loops, for the silica derivates the hysteresis width increases up to 37–42 K. This probes the efficiency of the silica shell to promote interparticle interactions and enhance cooperativity effects. Tomographic studies of the FeHTrz@SiO2 nanoparticles reveal a core–shell structure with the pure FeHTrz polymer wrapped into a thin shell of pure silica. Taking advantage of the chemical properties of the silica shell, these hybrid nanoparticles were coated with a dansyl derivate fluorophore whose luminescence properties can be adjusted by the spin state of the SCO polymer. Time-dependent luminescence studies reveal the existence of a non-radiative energy transfer (Förster type) between the organic fluorophore and the Fe(II)-low spin ions. These nanoparticles have also been functionalized with thiol groups allowing them to be deposited onto a gold surface in a controlled manner

A high-pressure crystallographic and magnetic study of Na5[Mn(l-tart)2]·12H2O (l-tart = l-tartrate)

The crystal structure and magnetic properties of the compound Na5[Mn(L-tart)2]•12H2O (1, L-tart = L-tartrate) have been investigated over the pressure range 0.34 – 3.49 GPa. The bulk modulus of 1 has been determined as 23.9(6) GPa, with a compression of the coordination spheres around the Na+ ions observed. 1 is therefore relatively incompressible, helping it to retain its magnetic anisotropy under pressure

Electronic structure of a Mn-6 (S=4) single molecule magnet grafted on Au(111)

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