Using a set of pyrazolate-based dinucleating ligands with thioether sidearms and a set of different carboxylates, seven tetranuclear nickel(II) complexes of types [L2Ni4(N3)3(O2CR)2](ClO4) (1) and [L2Ni4(N3)(O2CR)4](ClO4) (2) featuring an unprecedented central mu4-1,1,3,3-azide could be isolated and fully characterized. X-ray crystal structures are discussed for 1a,b,e and 2b. The mu4-1,1,3,3-azide is symmetric in all cases except 1a but exhibits distinct binding modes with significantly different Ni-N(azide)-Ni angles and Ni-NNN-Ni torsions in type 1 and 2 complexes, which indicates high structural flexibility of this novel bridging unit. Also, IR-spectroscopic signatures and magnetic properties are distinct for type 1 and 2 complexes. Magnetic data for 1a,b,d,e and 2a,b were investigated and analyzed in a three-J approach. The only model that gave a satisfactory fit for all type 1 complexes includes one dominant antiferromagnetic coupling and two ferromagnetic interactions (one large and one smaller), indicating some degree of frustration. On the basis of magneto-structural correlations for end-on and end-to-end azide linkages, it is reasonable to assign the antiferromagnetic interaction to the intradimer exchange along the pyrazolate and the end-to-end linkage of the mu4-azide. Overall, the magnitude of the coupling constants differs significantly for the two distinct types of compounds, 1 or 2, and depends on the individual geometric details of the Ni4 array and the mu4-1,1,3,3-azide.
Electron spin resonance and magnetization data in magnetic fields up to 55 T of a novel multicenter paramagnetic molecular complex [L2Ni4(N3)(O2C Ada)4](Cl O4) are reported. In this compound, four Ni centers each having a spin S = 1 are coupled in a single molecule via bridging ligands (including a µ4-azide) which provide paths for magnetic exchange. Analysis of the frequency and temperature dependence of the ESR signals yields the relevant parameters of the spin Hamiltonian, in particular the single ion anisotropy gap and the g factor, which enables the calculation of the complex energy spectrum of the spin states in a magnetic field. The experimental results give compelling evidence for tuning the ground state of the molecule by magnetic field from a nonmagnetic state at small fields to a magnetic one in strong fields owing to the spin level crossing at a field of ∼ 25 T.
We report the synthesis, crystal structure and magnetic properties of the S=1 2-leg spin-ladder compound Na2Ni2(C2O4)3(H2O)2. The magnetic properties were examined by magnetic susceptibility and pulsed high field magnetization measurements. The magnetic excitations have been measured in high field high frequency ESR. Although the Ni(II) ions form structurally a 2-leg ladder, an isolated dimer model consistently describes the observations very well. The analysis of the temperature dependent magnetization data leads to a magnetic exchange constant of J = 43 K along the rungs of the ladder and an average value of the g-factor of 2.25. From the ESR measurements, we determined the single ion anisotropy to D = 11.5 K. The validity of the isolated dimer model is supported by Quantum Monte Carlo calculations, performed for several ratios of interdimer and intradimer magnetic exchange and taking into account the experimentally determined single ion anisotropy. The results can be understood in terms of the different coordination and superexchange angles of the oxalate ligands along the rungs and legs of the 2-leg spin ladder.
We present a clamp-type pressure cell for high energy x-ray diffraction. The pressure cell was specifically designed for studies of weak superstructure reflections at low temperatures in transition metal oxides, resulting from, e.g., charge density modulations. Using a photon energy of E = 100 keV, the bulk properties of single crystals with a volume of typically 2 -5 mm 3 can be studied in transmission geometry. To demonstrate the performance of the pressure cell, we present data on the charge stripe order in the high-temperature superconductor La 1.875 Ba 0.125 CuO 4 .
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