Spin state dependence of electrical conductivity of spin crossover materials

We studied the spin state dependence of the electrical conductivity of the spin crossover compound [Fe(Htrz)2(trz)](BF4) (Htrz = 1H-1,2,4-triazole) by means of dc electrical measurements. The low spin state is characterized by higher conductance and lower thermal activation energy of the conductivity, when compared to the high spin state

Electrical properties and non-volatile memory effect of the [Fe(HB(pz)3)2] spin crossover complex integrated in a microelectrode device

We report on the deposition of thin films of the [Fe(HB(pz)3)2] (pz = pyrazolyl) molecular spin crossover complex by thermal evaporation. By means of impedance measurements and Raman microspectroscopy, we show that the films maintain the structure and properties of the bulk material. The conductivity of the films decreases by ca. 2 orders of magnitude when the freshly deposited compound goes through a first (irreversible) thermal phase change above ca. 380 K. This property can be exploited as a non-volatile (read-only) memory effect

Effect of ligand substitution in [Fe(H-trz)2(trz)]BF4 spin crossover nanoparticles

Spin crossover iron(II) 1,2,4-triazole-based coordination compounds in the form of nanoparticles were prepared using a reverse microemulsion technique. Ligand substitution approach was applied to decrease the spin crossover temperature towards room temperature in the well-known [Fe(Htrz)2(trz)]BF4 complex. The compositions of the particles were determined by elemental analysis and thermogravimetry. The morphology was monitored by transition electron microscopy (TEM). The effect associated with the ligand substitution was investigated by optical and magnetic measurements. Transition temperature has been reduced by 33 K comparing the unsubstituted sample to that with 5 % substitution

Charge Transport and Electrical Properties of Spin Crossover Materials: Towards Nanoelectronic and Spintronic Devices

In this paper, we present a comprehensive review of research on electrical and charge transport properties of spin crossover complexes. This includes both the effect of spin-state switching on the dielectric permittivity and electrical conductivity of the material and vice versa the influence of an applied electrical field (or current) on the spin-state of the system. The survey covers different size scales from bulk materials and thin films to nanoparticles and single molecules and embraces the presentation of several device prototypes and hybrid materials as well

Coupling Mechanical and Electrical Properties in Spin Crossover Polymer Composites

Spin crossover particles of formula[Fe{(Htrz)2(trz)}0.9(NH2-trz)0.3](BF4)1.1 and average size of 20 nm ± 8 nm are homogeneously dispersed in poly(vinylidene,fluoride-co-trifluoro-ethylene), P(VDF-TrFE), and poly(vinylidene fluoride)PVDF) matrices to form macroscopic (cm-scale), freestanding, and flexible nanocomposite materials. The composites exhibit concomitant thermal expansion and discharge current peaks on cycling around the spin transition temperatures, i.e., new “product properties” resulting from the synergy between the particles and the matrix. Poling the P(VDF-TrFE) (70–30 mol%) samples loaded with 25 wt% of particles in 18 MV m−1 electric field results in a piezoelectric coefficient d33 = −3.3 pC N−1. The poled samples display substantially amplified discharges and altered spin transition properties. Analysis of mechanical and dielectric properties reveals that both strain (1%) and permittivity (40%) changes in the composite accompany the spin transition in the particles, giving direct evidence for strong electromechanical couplings between the components. These results provide a novel route for the deployment of molecular spin crossover materials as actuators in artificial muscles and generators in thermal energy harvesting devices

Spatiotemporal dynamics of the spin transition in [Fe(HB(tz)3_3)2_2] single crystals

The spatiotemporal dynamics of the spin transition have been thoroughly investigated in single crystals of the mononuclear spin-crossover (SCO) complex [Fe(HB(tz)$_3$)$_2$] (tz=1,2,4-triazol-1-yl) by optical microscopy. This compound exhibits an abrupt spin transition centered at 334 K with a narrow thermal hysteresis loop of ∼ 1 K (first-order transition). Most single crystals of this compound reveal exceptional resilience upon repeated switching (several hundred cycles), which allowed repeatable and quantitative measurements of the spatiotemporal dynamics of the nucleation and growth processes to be carried out. These experiments revealed remarkable properties of the thermally induced spin transition: high stability of the thermal hysteresis loop, unprecedented large velocities of the macroscopic low-spin/high-spin phase boundaries up to 500 µm/s, and no visible dependency on the temperature scan rate. We have also studied the dynamics of the low-spin → high-spin transition induced by a local photothermal excitation generated by a spatially localized (Ø=2µm) continuous laser beam. Interesting phenomena have been evidenced both in quasistatic and dynamic conditions (e.g., threshold effects and long incubation periods, thermal activation of the phase boundary propagation, stabilization of the crystal in a stationary biphasic state, and thermal cutoff frequency). These measurements demonstrated the importance of thermal effects in the transition dynamics, and they enabled an accurate determination of the thermal properties of the SCO compound in the framework of a simple theoretical model

Re-investigation of the spin crossover phenomenon in the ferrous complex [Fe(HB(pz)3)2]

The temperature dependence of the magnetic susceptibility, optical reflectivity and electrical conductivity of [Fe(HB(pz)3)2] (pz = pyrazolyl) revealed irreversible changes in the material during the low-spin to high-spin transition when the ‘‘as-prepared’’ sample was heated above B400 K for the first time. During this first heating sequence, the initially fine powder sample became coarse, and its crystal structure changed from tetragonal to monoclinic. Single-crystals of the monoclinic form suitable for X-ray analysis could be isolated after the first thermal cycle, and their structure was resolved in the P21/n (Z = 4) space group. Successive cooling and heating cycles did not lead to further modification of the crystal structure, and the temperature dependence of the physical properties remained invariable. Remarkably, the electrical conductivity of the sample measured at 293 K dropped from 6.1 108 to 2.1 1011 S m1 following the first thermal cycle—suggesting possible applications of this material in read-only memory devices (ROM)