A Mixed-Valence Mixed-Spin Prussian-Blue-Like Heptanuclear Complex

One-dimensional Ising-like systems: an analytical investigation of the static and dynamic properties, applied to spin-crossover relaxation

We investigate the dynamical properties of the 1-D Ising-like Hamiltonian taking into account short and long range interactions, in order to predict the static and dynamic behavior of spin crossover systems. The stochastic treatment is carried out within the frame of the local equilibrium method [1]. The calculations yield, at thermodynamic equilibrium, the exact analytic expression previously obtained by the transfer matrix technique [2]. We mainly discuss the shape of the relaxation curves: (i) for large (positive) values of the short range interaction parameter, a saturation of the relaxation curves is observed, reminiscent of the behavior of the width of the static hysteresis loop [3]; …

Raman spectroscopy of the high- and low-spin states of the spin crossover complex Fe(phen)2(NCS)2: an initial approach to estimation of vibrational contributions to the associated entropy change

Abstract Raman spectra of the spin-crossover complex Fe(phen)2(NCS)2 in the solid state have been recorded at 785 nm as a function of temperature to investigate the contribution of intramolecular vibrations to the entropy change, ΔS, associated with spin crossover. The modes of major interest for estimating the contribution lie in the range 100–500 cm−1, where the largest qualitative changes with temperature in the Raman spectra were observed. Analysis of these data, with the working assumption of an average frequency in this range as representative of the 15 distortion modes of an idealised FeN6 octahedron, leads to the conclusion that the intramolecular vibrations represent a primary cont…

Analytical solution of 1D Ising-like systems modified by weak long range interaction

It is well-known that 1D systems with only nearest neighbour interaction exhibit no phase transition. It is shown that the presence of a small long range interaction treated by the mean field approximation in addition to strong nearest neighbour interaction gives rise to hysteresis curves of large width. This situation is believed to exist in spin crossover systems where by the deformation of the spin changing molecules, an elastic coupling leads to a long range interaction, and strong bonding between the molecules in a chain compound leads to large values for nearest neighbour interaction constants. For this interaction scheme an analytical solution has been derived and the interplay betwe…

A new 3-D polymeric spin transition compound: [tris(1,4-bis(tetrazol-1-yl)butane-N1,N 1′)iron(II)] bis(perchlorate)

A series of novel polymeric compounds of formula [M(btzb)3][ClO4]2 (Mll = Fe, Ni or Cu) with btzb = 1,4-bis-(tetrazol-1-yl)butane have been prepared and their physical properties investigated. The btzb ligand has been prepared and its crystal structure determined, together with a tentative crystal structure of the 3-D compound [Fe(btzb)3][ClO4]2. The model of the latter shows two symmetry-related, interpenetrating Fe-btzb networks in which the iron(II) ions approach each other as close as 8.3 and 9.1 A. This supramolecular catenane undergoes a sharp thermal spin transition around 160 K with hysteresis (20 K) along with a pronounced thermochromic effect. The spin crossover behaviour has been…

Spin crossover in a catenane supramolecular system.

The compound [Fe(tvp)(2)(NCS)(2)] . CH(3)OH, where tvp is 1,2-di-(4-pyridyl)-ethylene, has been synthesized and characterized by x-ray single-crystal diffraction. It consists of two perpendicular, two-dimensional networks organized in parallel stacks of sheets made up of edge-shared [Fe(II)](4) rhombuses. The fully interlocked networks define large square channels in the [001] direction. Variable-temperature magnetic susceptibility measurements and Mossbauer studies reveal that this compound shows low-spin to high-spin crossover behavior in the temperature range from 100 to 250 kelvin. The combined structural and magnetic characterization of this kind of compound is fundamental for the inte…

Total free energy of a spin-crossover molecular system

The free energy of spin-crossover molecular systems studied so far deal with the inner degrees of freedom of the spin-crossover molecules and a variety of interaction schemes between the molecules in the high spin (HS) and low spin (LS) states. Different types of transition curves, gradual, abrupt, hysteresis, and also two step transitions have been simulated or even satisfactorily fitted to experimental data. However, in the last decade spin transition curves were measured, especially under pressure, which could not be explained within these theoretical models. In this contribution the total free energy of an anharmonic lattice incorporating spin-crossover molecules which have a certain mi…