Magnetization Plateaus

Abstract This review reports on the study of the interplay between magnetic coupling and spin transition in 2,2 -bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. The coexistence of both phenomena has been observed in [Fe(bpym)(NCS)2]2(bpym), [Fe(bpym)(NCSe)2]2(bpym) and [Fe(bt)(NCS)2]2(bpym) (bpym = 2,2 -bipyrimidine, bt = 2,2 -bithiazoline) by the action of external physical perturbations such as heat, pressure or electromagnetic radiation. The competition between magnetic exchange and spin crossover has been studied in [Fe(bpym)(NCS)2]2(bpym) at 0.63 GPa. LIESST experiments carried out on [Fe(bpym)(NCSe)2]2(bpym) and [Fe(bt)(NCS)2]2(bpym) at 4.2 K have shown that it is possible to generate dinuclear molecules with different spin states in this class of compounds. A special feature of the spin crossover process in the dinuclear compounds studied so far is the plateau in the spin transition curve. Up to now, it has not been possible to explore with a microscopic physical method the nature of the species... 

Keywords Spin crossover Dinuclear complexes Two-step transition Plateau Magnetic field Mossbauer spectroscopy... 

The special feature of the spin crossover process in all bpym-bridged dinuclear compounds studied so far is the occurrence of a plateau in the spin transition curve. A reasonable assumption to account for this observation is that a thermal spin transition takes place successively in the two metal centres. However, it cannot be excluded that spin transition takes place simultaneously in the dinuclear units leading directly from [HS—HS] pairs to [LS-LS] pairs with decreasing temperature. Therefore, two possible conversion pathways for [HS—HS] pairs with decreasing temperature may be proposed [HS—HS]<->[HS—LS]<->[LS—LS] or [HS-HS] [LS-LS]. The differentiation of the existence of the [LS—LS], [HS—LS], and [HS—HS] spin pairs is not trivial and has recently been solved experimentally by utilisation of magnetisation versus magnetic field measurements as a macroscopic tool [9], and by Mossbauer spectroscopy in an applied magnetic field as a microscopic tool [11]. 

Fig. 16 57Fe Mossbauer spectra of [Fe(phdia)(NCS)2]2(phdia) at room temperature (a), at 100 K after subsequent slow cooling (<1 K/min) (b), at 4.2 K after further slow cooling (c), at 4.2 K after rapid cooling from the plateau with a rate of 100 K/min (d), at 4.2 K in a magnetic field of 50 kOe after quenching from the plateau (e). LS in [HS-LS] and [LS-LS] pairs (grey), HS in [HS-LS] pairs (light grey)...

Fig. 18 Representative scheme of the enthalpy of [HS—HS], [HS—LS] and [LS—LS] pairs (a) and comparative magnetic behaviour of (bt, S) and [Fe(phdia)(NCS)2]2phdia (b). The composition of the plateau region as a percentage of the pairs is indicated...

Three characteristics of the MRD profile change when the protein is hydrated with either H2O or D2O. Both terms of Eq. (6) are required to provide an accurate fit to the data. The second or perpendicular term dominates once the transverse modes become important. The power law for the MRD profile is retained, but the exponent takes values between 0.78 and 0.5 depending on the degree of hydration. A low frequency plateau is apparent for samples containing H2O which derives from two sources the field limitation of the local proton dipolar field as mentioned above, and from limitations in the magnetization transfer rates that may be a bottleneck in bringing the liquid spins into equilibrium with the solid spins. 

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