Oliver Waldmann

Coexistence of Distinct Single‐Ion and Exchange‐Based Mechanisms for Blocking of Magnetization in a CoII2DyIII2 Single‐Molecule Magnet

Two ways to relax: A defect-dicubane Co2Dy2 single-molecule magnet (SMM) displays slow relaxation of magnetization with a blocking temperature of 22 K (at 1500 Hz), the highest reported for a 3d–4f-based SMM. Analysis of the relaxation reveals two distinct blocking regimes, one of which is intraionic, localized on the DyIII ions, while the other is exchange-based.

Modifying the properties of 4f single-ion magnets by peripheral ligand functionalisation

We study the ligand-field splittings and magnetic properties of three ErIII single-ion magnets which differ in the peripheral ligand sphere but exhibit similar first coordination spheres by inelastic neutron scattering (INS) and SQUID magnetometry. The INS spectra of the three compounds are profoundly different pointing at a strong response of the magnetic behavior to minor structural changes, as they are e.g. encountered when depositing molecules on surfaces. The observation of several magnetic excitations within the J = 15/2 ground multiplet together with single-crystal magnetic measurements allows for the extraction of the sign and magnitude of all symmetry-allowed Stevens parameters. The parameter values and the energy spectrum derived from INS are compared to the results of state-of-the-art ab initio CASSCF calculations. Temperature-dependent alternating current (ac) susceptibility measurements suggest that the magnetisation relaxation in the investigated temperature range of 1.9 K < T < 5 K is dominated by quantum tunnelling of magnetisation and two-phonon Raman processes. The possibility of observing electron paramagnetic resonance transitions between the ground-state doublet states, which can be suppressed in perfectly axial single-ion magnets, renders the studied systems interesting as representations of quantum bits.

Combined Magnetic Susceptibility Measurements and 57Fe Mössbauer Spectroscopy on a Ferromagnetic {FeIII4Dy4} Ring

Ferromagnetic interactions in an Fe4Dy4 single-molecule magnet were studied using a combination of magnetic susceptibility measurements (see diagram; inset: cluster core) and 57Fe Mossbauer spectroscopy.

Modelling the Magnetic Behaviour of Square-Pyramidal CoII5 Aggregates: Tuning SMM Behaviour through Variations in the Ligand Shell

Three new mu4-bridged Co(II)5 clusters with similar core motifs have been synthesised with the use of N-tert-butyldiethanolamine (tbdeaH2) and pivalic acid (piv): [Co(II)5(mu4-N3)(tbdea)2(mu-piv)4(piv)(CH3CN)2].CH3CN (1), [Co(II)5(mu4-Cl)(Cl)(tbdea)2(mu-piv)4(pivH)2] (2) and [Co(II)5(mu4-N3)(Cl)(tbdea)2(mu-piv)4(pivH)2] (3). Magnetic measurements were performed for all three compounds. It was found that while the chloride-bridged cluster 2 does not show an out-of-phase signal, which excludes single-molecule magnet (SMM) behaviour, the azide-bridged compounds 1 and 3 show out-of-phase signals as well as frequency dependence of the ac susceptibility, as expected for SMMs. We confirmed that 1 is a SMM with zero-field quantum tunnelling of the magnetisation at 1.8 K. Compound 3 is likely a SMM with a blocking temperature well below 1.8 K. We established a physical model to fit the chiT versus T and M versus B curves of the three compounds to reproduce the observed SMM trend. The analysis showed that small changes in the ligand shell modify not only the magnitude of exchange constants, but also affect the J and g matrices in a non-trivial way.

Direct observation of a ferri-to-ferromagnetic transition in a fluoride-bridged 3d–4f molecular cluster

We report on the synthesis, crystal structure and magnetic characterisation of the trinuclear, fluoride-bridged, molecular nanomagnet [Dy(hfac)3(H2O)–CrF2(py)4–Dy(hfac)3(NO3)] (1) (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone, py = pyridine) and a closely related dinuclear species [Dy(hfac)4–CrF2(py)4]·½CHCl3 (2). Element-specific magnetisation curves obtained on 1 by X-ray magnetic circular dichroism (XMCD) allow us to directly observe the field-induced transition from a ferrimagnetic to a ferromagnetic arrangement of the Dy and Cr magnetic moments. By fitting a spin-Hamiltonian model to the XMCD data we extract a weak antiferromagnetic exchange coupling of j = −0.18 cm−1 between the DyIII and CrIII ions. The value found from XMCD is consistent with SQUID magnetometry and inelastic neutron scattering measurements. Furthermore, alternating current susceptibility and muon-spin relaxation measurements reveal that 1 shows thermally activated relaxation of magnetisation with a small effective barrier for magnetisation reversal of Δeff = 3 cm−1. Density-functional theory calculations show that the Dy–Cr couplings originate from superexchange via the fluoride bridges.

Synthesis, characterization, and single-molecule metamagnetism of new Co(II) polynuclear complexes of pyridine-2-ylmethanol.

The reaction between pyridine-2-ylmethanol (HL), anhydrous CoCl(2) and NaH afforded polynuclear Co(II) complexes [Co(7)(L)(12)]Cl(2) (1), [Co(6)Na(L)(12)]Cl (2) and [Co(4)Cl(2)(L)(6)] (3), depending on the HL:CoCl(2) ratio set in the reaction. The core structures of the centrosymmetric complexes 1 and 2 are of the M@Co(6) type (M = Co or Na, respectively) with a coplanar arrangement of the metals whereas that of centrosymmetric 3 is of an incomplete dicubane type. The experimental conditions allowing interconversions between these polynuclear complexes have been determined, which provides a more rational control of their synthesis. Thus, 1 transforms to 3 when reacted with CoCl(2) in a 1 : 1 ratio, whereas the same reaction performed with a large excess of CoCl(2) gave the tetranuclear pseudo-cubane complex [Co(4)(L)(4)Cl(2)(MeOH)(4)] upon recrystallization. Conversely, 1 was isolated from the reaction of 3 with HL and NaH. The crystal structure of these compounds is reported, along with the magnetic behaviour of 1 and 3. The analysis of the magnetism using the effective spin-1/2 Hamiltonian approach revealed single-molecule metamagnetic behavior in 3.

Field-dependent anisotropy change in a supramolecular Mn(II)- [3 x 3] grid.

The magnetic anisotropy of a novel Mn(II)- [3x3] grid complex was investigated by means of high-field torque magnetometry. Torque vs field curves at low temperatures demonstrates a ground state with S>0 and exhibits a torque step due to a field-induced level crossing at B(*) approximately 7.5 T, accompanied by an abrupt change of magnetic anisotropy from easy-axis to hard-axis types. These observations are discussed in terms of a spin Hamiltonian formalism.

Assessment of the Anisotropy in the Molecule Mn19 with a High-Spin Ground State S = 83/2 by 35 GHz Electron Paramagnetic Resonance

35 GHz electron paramagnetic resonance experiments on a powder sample of the magnetic molecule Mn 19 with a high-spin ground state S = 83/2 are presented. At low temperatures, the data are well described by the simulated spectra for an isolated spin with a zero-field-splitting parameter D = 0.004 cm (-1), which is, in particular, positive. Hence, Mn 19 is not a single-molecule magnet; the previously observed magnetic hysteresis at ultralow temperatures is likely due to intermolecular dipolar interactions.

Elementary excitations in the cyclic molecular nanomagnet Cr8

Combining recent and new inelastic neutron scattering data for the molecular cyclic cluster Cr8 produces a deep understanding of the low lying excitations in bipartite antiferromagnetic Heisenberg rings. The existence of the L band, the lowest rotational band, and the E band, essentially spin wave excitations, is confirmed spectroscopically. The different significance of these excitations and their physical nature is clearly established by high-energy and Q-dependence data.

Magnetic anisotropy of a supramolecular Cu(II) [3×3] grid

Abstract The magnetic anisotropy of the nona-Cu(II) [3×3] grid structure [Cu 9 (2POAP–H) 6 ](NO 3 ) 12 ·9H 2 O was investigated by means of torque magnetometry. The analysis of the high-field part of torque vs. field curves measured at 1.75 K allowed a precise determination of all anisotropy parameters of the ground state. These could be related to the magnetic parameters of the microscopic Hamiltonian by a suitable perturbation theoretical treatment. We found strong evidence for a sizeable anisotropic exchange interaction. The observed anisotropy of the g -factor could not be explained by simple ligand field arguments which is attributed to the unusual quasi-octahedral coordination environment of the Cu ions.