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Redetermination of Zero-Field Splitting in [Co(qu)2Br2] and [Ni(PPh3)2Cl2] Complexes

Abstract

A mononuclear CoII complex, [Co(qu)2Br2], and NiII complex, [Ni(PPh3)2Cl2], (qu = quinoline, PPh3 = triphenylphosphine) have been reinvestigated. Their crystal and molecular structures are reported along with IR and UV-Vis spectra. Magnetism of both complexes has been studied by using the DC SQUID magnetometry. These complexes exhibit a moderate magnetic anisotropy expressed by zero-field splitting parameter D. The D-value is positive for both complexes with D/hc = +5.94 cm−1 and D/hc = +12.76 cm−1, that is also confirmed by ab initio calculations.

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Magnetic response of bovine spleen

Abstract

Bovine spleen has been used as a sample for deep magnetochemical investigation. Temperature dependence of the magnetic susceptibility and field dependence of the magnetization reveal a paramagnetic behaviour that violates the Curie law. The zero-field cooled magnetization and field cooled magnetization experiments show the bifurcation point at ca T C = 20 K and the blocking temperature T B = 10 K confirming a dominating portion of ferritin along with the organic tissue. There is a remnant magnetization at temperature below 20 K and the search for the magnetic hysteresis was positive.

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Magnetostructural Relationships For Fe(III) Spin Crossover Complexes

Abstract

Structural data for fifteen complexes of Fe(III) of a general formula [FeL5X], with pentadentate Schiff-base ligands L5 and unidentate coligands X, were subjected to a statistical analysis. The multivariate methods such as Pearson correlation, cluster analysis and principal component analysis split the data into two clusters depending upon the low-spin and/or high-spin state of the complex at the temperature of the X-ray experiment. Some of these complexes exhibit a thermally induced spin crossover. The numerical analysis of the magnetic susceptibility and magnetization data for an enlarged set of Fe(III) spin crossover systems yields the enthalpy ΔH and entropy ΔS of the transition along with the transition temperature T 1/2 and the solid state cooperativeness. The thermodynamic data show a mutual relationship manifesting itself by linear ΔS vs ΔH and T 1/2 vs ΔH correlations.

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Utilization of the Spin Symmetry in Fitting the Magnetic Data lor Large Exchange Clusters

Abstract

The Heisenberg Hamiltonian appropriate to exchange clusters commutes with the square of the total spin ant its third component. Therefore in studying the exchange coupled clusters of medium/high nuclearity the spin quantum number S can be utilized in factoring of large interaction matrices (dimension of which is 104 - 105). Then the blocks of much lower size can be diagonalized using the desktop computers. To this end, the eigenvalues form the partition function Z(T,B) from which all thermodynamic properties, including the magnetization M(B,T0) and the magnetic susceptibility χ(T,B0), can be reconstructed. The matrix elements of the interaction operators in the coupled basis set of spin kets have been generated with the help of the irreducible tensor operators for a loop for S = Smin until S = Smax. In addition to the modelling of energy levels for different topologies, a fitting of magnetic data is exemplified by a number of examples like [Fe6] and [Mn3Cr4] systems

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