Spin-crossover Transition Research Articles

First indirect experimental evidence and theoretical discussion of giant refrigeration capacity through the reversible pressure induced spin-crossover phase transition

We report on the giant barocaloric effect and refrigerant capacity in the [Fe(pzt)6](PF6)2 (pzt = 1-propyltetrazole) spin-crossover material. The refrigerant capacity in [Fe(pzt)6](PF6)2 is RC = 1380 J kg−1, 5 times higher than the big value reported in (NH4)2SO4, upon pressure variation ΔP = 1 kbar. This huge caloric effect is ascribed to the coupling interactions between the crystal lattice (phonons) and the order parameter (γHS) that describes the molar fraction of high spin molecules (Fe+2N6)-(t2g4eg2) in [Fe(pzt)6](PF6)2. Our theoretical entropy includes the lattice, electronic and configurational coupled-contributions and was obtained from a microscopic model. A new methodology to obtain the barocaloric effect potentials is presented using a proper thermodynamic Maxwell relation for spin-crossover systems. The experimental results, for the isothermal entropy change, were calculated from the pressure dependence of γHS data. Besides, the determination of molecular volume change between high and low spin states through caloric measurements was discussed.

Contribution of Coulomb Interactions to a Two-Step Crystal Structure Phase Transformation Coupled with a Significant Change in Spin Crossover Behavior for a Series of Charged FeII Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine.

A series of [FeII(L)2](BF4)2 compounds were structurally and physically characterized (L = 2,6-bis(2-methylthiazol-4-yl)pyridine). A crystal structure phase transformation from dihydrate compound 1 to anhydrous compound 3 through partially hydrated compounds 2 and 2' upon dehydration was found. Compounds 1 and 3 exhibited a gradual spin crossover (SCO) conversion, whereas compounds 2 and 2' demonstrated two-step and one-step abrupt SCO transitions, respectively. An X-ray single-crystal structural analysis revealed that one-dimensional and two-dimensional Fe cation networks linked by π stacking and sulfur-sulfur interactions were formed in 1 and 3, respectively. A thermodynamic analysis of the magnetic susceptibility for 1, 2', and 3 suggests that the enthalpy differences may govern SCO transition behaviors in the polymorphic compounds 2' and 3. A structural comparison between 1 and 3 indicates that the SCO behavior variations and crystal structure transformation in the present [FeII(L)2](BF4)2 compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.

Temperature-, Light-, and Soft X-ray-Induced Spin Crossover in a Single Layer of FeII-Pyrazolylborate Molecules in Direct Contact with Gold

Understanding the properties of spin-crossover molecules in direct contact with metals is crucial for their future integration in electronic and spintronic devices. By X-ray absorption spectroscopy, we investigate the properties of FeII((3,5-(CH3)2Pz)3BH)2 molecules in the form of monolayer islands on a metallic substrate, namely, Au(111). We demonstrate that the spin-crossover transition can be thermally induced from the high spin state to a mixed spin state phase containing one-third of high-spin-state and two-thirds of low-spin-state molecules in agreement with previous work by scanning tunneling microscopy. In addition, at 4.4 K, the spin crossover from the low spin state to the high spin state can also be induced by X-ray and by light excitations.

Ab Initio Ligand Field Molecular Mechanics and the Nature of Metal-Ligand π-Bonding in Fe(II) 2,6-di(pyrazol-1-yl)pyridine Spin Crossover Complexes.

A ligand field molecular mechanics (LFMM) force field has been constructed for the spin states of [Fe(bpp)2 ]2+ (bpp=2,6-di(pyrazol-1-yl)pyridine) and related complexes. A new charge scheme is employed which interpolates between partial charges for neutral bpp and protonated [H3 bpp]3+ to achieve a target metal charge. The LFMM angular overlap model (AOM) parameters are fitted to fully ab initio d orbital energies. However, several AOM parameter sets are possible. The ambiguity is resolved by calculating the Jahn-Teller distortion mode for high spin, which indicates that in [Fe(bpp)2 ]2+ pyridine is a π-acceptor and pyrazole a weak π-donor. The alternative fit, assumed previously, where both ligands act as π-donors leads to an inconsistent distortion. LFMM optimisations in the presence of [BF4 ]- or [PF6 ]- anions are in good agreement with experiment and the model also correctly predicts the spin state energetics for 3-pyrazolyl substituents where the interactions are mainly steric. However, for 4-pyridyl or 4-pyrazolyl substituents, LFMM only treats the electrostatic contribution which, for the pyridyl substituents, generates a fair correlation with the spin crossover transition temperatures, T1/2 , but in the reverse sense to the dominant electronic effect. Thus, LFMM generates its smallest spin state energy difference for the substituent with the highest T1/2 . One parameter set for all substituted bpp ligands is insufficient and further LFMM development will be required.

Pressure-induced two-step spin crossover in a double-layered elastic model

We study the two-step spin crossover in a double-layered elastic model based on transition metal complexes each taking high spin (HS) and low spin (LS) states. Here, only the simplest elastic interactions between adjacent molecules are considered and the system is exposed to the external pressure within the framework of $NPT$-Monte Carlo method. As a certain amount of pressure is applied, the first order thermal transition between uniform HS and LS phases transforms to a two-step transition with an emergent intermediate spin (IS) phase, where the HS and LS molecules are paired face to face between layers and form diagonally striped clusters within the layer. The difference in the size of HS and LS molecules is reflected both in the elastic interactions and in the enthalpy, and the IS phase could gain the latter over the loss of the former by significantly reducing its volume. The present pressure effect is interpreted to the chemical one in double-layered transition metal materials, which actually reveals a variety of multistep spin crossover transitions relevant to our numerical result.

Nontrivial phase diagram for an elastic interaction model of spin crossover materials with antiferromagnetic-like short-range interactions

We study the phase diagram of an elastic interaction model for spin crossover (SC) materials with antiferromagnetic-like short-range interactions. In this model, the interplay between the short-range interaction and the long-range interaction of elastic origin causes complex phase transitions. For relatively weak elastic interactions, the phase diagram is characterized by tricritical points, at which antiferromagnetic (AF) -like and ferromagnetic (F) -like spinodal lines and a critical line merge. On the other hand, for relatively strong elastic interactions, unusual ``horn structures,'' which are surrounded by the F-like spinodal lines, disorder (D) spinodal lines, and the critical line, are realized at higher temperatures. These structures are similar to those obtained in our previous study [Phys. Rev. B 93, 064109 (2016)] of an Ising antiferromagnet with infinite-range ferromagnetic interactions, and we find universal features caused by the interplay between the competing short-range and long-range interactions. The long-range interaction of elastic origin is irrelevant (inessential) for the critical line. In contrast, the AF-like, F-like, and D spinodal lines result from the long-range interaction of elastic origin. This difference causes qualitatively different features of domain formation or nucleation of the new phase: clustering occurs in the former case, while clustering is absent in the latter. Based on the phase diagrams, we discuss the patterns and clustering features of two-step SC transitions, in which the AF-like phase is realized in the intermediate temperature region.

Locking and Unlocking the Molecular Spin Crossover Transition.

The Fe(II) spin crossover complex [Fe{H2 B(pz)2 }2 (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO2 and Al2 O3 , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C6 H2 (-⋯ NH2 )2 (-⋯ O)2 . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H2 B(pz)2 }2 (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.

Spin-State Patterning in an Iron(II) Tripodal Spin-Crossover Complex.

A mononuclear iron(II) complex that displays a gradual two-step spin-crossover (SCO) transition is reported. The intermediate plateau (IP) occurs between HS0.40LS0.60 and HS0.30LS0.70 (HS = high spin; LS = low spin) ratios over the region of ca. 190–170 K. A phase change occurs at the IP, breaking the symmetry, resulting in six independent SCO sites compared to one at the 100% HS and LS plateau regions, respectively. Variable-temperature X-ray photoelectron spectroscopy shows that the SCO behavior is completely reversible among the HS, IP, and LS regions. The results both confirm and extend the related results for the above system described by Halcrow et al. (KulmaczewskiR.; CespedesO.; HalcrowM. A.Gradual Thermal Spin-Crossover Mediated By a Reentrant Z′ = 1 → Z′ = 6 → Z′ = 1 Phase Transition, Inorg. Chem. 2017, 56, 3144−314828244751) in a recent report.

Quantum-Mechanical Study of the Reaction Mechanism for 2π-2π Cycloaddition of Fluorinated Methylene Groups.

Perfluorocyclobutyl polymers are thermally and chemically stable, may be produced without a catalyst via thermal 2π-2π cycloaddition, and can form block structures, making them suitable for commercialization of specialty polymers. Thermal 2π-2π cycloaddition is a rare reaction that begins in the singlet state and proceeds through a triplet intermediate to form an energetically stable four-membered ring in the singlet state. This reaction involves two changes in spin state and, thus, two spin-crossover transitions. Presented here are density functional theory calculations that evaluate the energetics and reaction mechanisms for the dimerizations of two different polyfluorinated precursors, 1,1,2-trifluoro-2-(trifluoromethoxy)ethane and hexafluoropropylene. The spin-crossover transition states are thoroughly investigated, revealing important kinetics steps and an activation energy for the gas-phase cycloaddition of two hexafluoropropene molecules of 36.9 kcal/mol, which is in good agreement with the experimentally determined value of 34.3 kcal/mol. It is found that the first carbon-carbon bond formation is the rate-limiting step, followed by a rotation about the newly formed bond in the triplet state that results in the formation of the second carbon-carbon bond. Targeting the rotation of the C-C bond, a set of parameters were obtained that best produce high molecular weight polymers using this chemistry.

Spatiotemporal Observation and Modeling of Remarkable Temperature Scan Rate Effects on the Thermal Hysteresis in a Spin-Crossover Single Crystal

The direct observation by optical microscopy of the thermally induced spin transition and the subsequent low-spin high-spin interface propagation inside the thermal hysteresis is a fascinating problem. The kinetic aspects of the spin crossover (SCO) transition investigated under various scan rates was mostly studied so far on powder sample which then average the kinetic effects of the thermal hysteresis. This problem is studied here on the robust spin-crossover single crystal [{Fe(NCSe)(py)2}2(m-bpypz)] for which we followed the dynamics of the thermal hysteresis at several controlled temperature scan rates. In addition to the expected shifts of the switching temperatures, sizable changes in the velocity of the high-spin (HS) low-spin (LS) interface dynamics are observed for the first time. Theoretical developments based on a spatiotemporal description of the SCO phenomenon using reaction diffusion equations including the heat balance between the crystal and its immediate environment are provided. We iden...

The Highly Conducting Spin-Crossover Compound Combining Fe(III) Cation Complex with TCNQ in a Fractional Reduction State. Synthesis, Structure, Electric and Magnetic Properties

Three systems [Fe(III)(sal2-trien)](TCNQ)n·X (n = 1, 2, X = MeOH, CH3CN, H2O) showing spin-crossover transition, conductivity and ferromagnetic coupling were synthesized and studied by X-ray diffraction, Montgomery method for resistivity, SQUID magnetometry and X-band EPR. Spin-spin interactions between local magnetic moments of Fe(III) ions and electron spins of organic TCNQ network were discovered and discussed within the framework of intermolecular superexchange coupling.

DFT Analysis of Spin Crossover in Mn(III) Complexes: Is a Two-Electron S = 2 to S = 0 Spin Transition Feasible?

Six-coordinate, rigorously octahedral d4 Mn(III) spin crossover (SCO) complexes are limited by symmetry to an S = 1 (intermediate spin, IS) to S = 2 (high spin, HS) transition. In order to realize the potential S = 0 to S = 2 transition, a lower symmetry and/or change in coordination number is needed, which we explore here computationally. First, a number of complexes are analyzed to develop a reliable and relatively fast DFT protocol for reproducing known Mn(III) spin state energetics. The hybrid meta-GGA functional TPSSh with a modest split valence plus polarization basis set and an empirical dispersion correction is found to predict correctly the ground spin state of Mn(III) complexes, including true low-spin (LS) S = 0 systems, with a range of donor sets including the hexadentate [N4O2] Schiff base ligands. The electronic structure design criteria necessary for realizing a ΔS = 2 SCO transition are described, and a number of model complexes are screened for potential SCO behavior. Five-coordinate trigonal-bipyramidal symmetry fails to yield any suitable systems. Seven-coordinate, approximately pentagonal bipyramidal symmetry is more favorable, and when a known pentadentate macrocyclic donor is combined with π-acceptor axial ligands, a novel Mn(III) complex, [Mn(PABODP)(PF3)2]3+ (PABODP = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene), is predicted to have the right spin state energetics for an S = 0 to S = 2 transition. Successful synthesis of such a complex could provide the first example of a ΔS = 2 SCO transition for d4 Mn(III). However, the combination of a rigid macrocycle and a high coordination number dilutes the stereochemical activity of the d electrons, leading to relatively small structural changes between HS and LS systems. It may therefore remain a challenge to realize strong cooperative effects in Mn(III) systems.

Influence of the interaction of polymeric chains on thermal transitions of Jahn—Teller exchange clusters in compounds of "breathing" crystal family

Based on the method of random field distribution functions in Ising magnets, for the first time a theoretical description of thermal transitions in Jahn—Teller exchange clusters is suggested, which takes into account the interactions of polymeric chains in "breathing" crystal compounds. It was shown that the inclusion of this interaction can lead to both an intensification of spin-crossover type cooperative transitions in exchange clusters and their deceleration. The approach in question is generalized to include non-Jahn—Teller metal impurities in "breathing" crystals, which suppress cooperative effects in thermal transitions of Jahn—Teller exchange clusters. The obtained results qualitatively reproduce the temperature dependencies of magnetic properties of solid solutions Cu1—x Ni x (hfac)2LR (hfac is hexafluoroacetylacetonate anion, ligand LR is nitronyl nitroxide radical with pyrazole substituent at the second position of the imidazoline ring) when R = Et.

Four-step iron(ii) spin state cascade driven by antagonistic solid state interactions.

A four-stepped cascade of Fe(ii) high spin (HS) to low spin (LS) states is demonstrated in a family of 2-D Hofmann materials, [Fe3II(saltrz)6(MII(CN)4)3]·8(H2O) (MII = Pd (1Pd ), Pt (1Pt ); saltrz = (E)-2-(((4H-1,2,4-triazol-4-yl)imino)methyl)phenol). Alongside the fully HS and LS Fe(ii) states, fractional spin state stabilization occurs at HS/LS values of 5/6, 2/3, and 1/6. This unconventional spin state periodicity is driven by the presence of multiple spin crossover (SCO) active Fe(ii) sites which are in subtly distinct environments driven by a network of antagonistic host-host and host-guest interactions. Alternating long- and short-range magnetostructural ordering is achieved over the five distinct spin state ratios HS1.0LS0.0, HS0.833LS0.167, HS0.667LS0.333, HS0.167LS0.833, and HS0.0LS1.0 owing to the flexibility of this 2-D interdigitated lattice topology interconnected by intermolecular interactions. A distinct wave-like spin state patterning is structurally evidenced for each intermediate phase.

Cooperative spin-crossover transition from three-dimensional purely π-stacking interactions in a neutral heteroleptic azobisphenolate FeIII complex with a N3O3 coordination sphere.

A novel neutral heteroleptic FeIII complex from two kinds of π-extended tridentate ligands was designed and prepared. The π-ligands formed a three-dimensional purely π-stacking interaction network. The present complex proved to be the first neutral spin-crossover (SCO) FeIII complex with a N3O3 coordination sphere exhibiting an abrupt SCO transition with a thermal hysteresis of 10 K and the light-induced excited spin-state trapping effect.

Influence of the dipolar interactions on the relative stability in spin crossover systems.

Molecules exhibiting a spin-crossover transition have been proposed for a number of applications such as molecular switches, spintronic tunable interfaces, and single molecule gates. Both the rational design of new spin-crossover systems and the improvement of the properties of the already existing ones require a theoretical understanding of the relative energy of the high (HS) and low spin state (LS) molecules in the solid-state. This has proved to be very challenging so far. Here, we shed some light on the importance of considering the symmetry and the geometry of the crystallographic cell to correctly evaluate the influence of the dipolar interactions on the relative energies of the molecular complex in both different spin states. Moreover, in the case of Fe(SCN)2 (phen)2 dipolar interactions are found to play an important role for the stabilization of the LS complex. © 2016 Wiley Periodicals, Inc.

Hysteretic Four‐Step Spin Crossover within a Three‐Dimensional Porous Hofmann‐like Material

AbstractMaterials that display multiple stepped spin crossover (SCO) transitions with accompanying hysteresis present the opportunity for ternary, quaternary, and quinary electronic switching and data storage but are rare in existence. Herein, we present the first report of a four‐step hysteretic SCO framework. Single‐crystal structure analysis of a porous 3D Hofmann‐like material showed long‐range ordering of spin states: HS, HS0.67LS0.33, HS0.5LS0.5, HS0.33LS0.67, and LS. These detailed structural studies provide insight into how multistep SCO materials can be rationally designed through control of host–host and host–guest interactions.

Hysteretic Four-Step Spin Crossover within a Three-Dimensional Porous Hofmann-like Material.

Materials that display multiple stepped spin crossover (SCO) transitions with accompanying hysteresis present the opportunity for ternary, quaternary, and quinary electronic switching and data storage but are rare in existence. Herein, we present the first report of a four-step hysteretic SCO framework. Single-crystal structure analysis of a porous 3D Hofmann-like material showed long-range ordering of spin states: HS, HS0.67 LS0.33 , HS0.5 LS0.5 , HS0.33 LS0.67 , and LS. These detailed structural studies provide insight into how multistep SCO materials can be rationally designed through control of host-host and host-guest interactions.

The Conducting Spin-Crossover Compound Combining Fe(II) Cation Complex with TCNQ in a Fractional Reduction State.

The radical anion salt [Fe{HC(pz)3}2](TCNQ)3 demonstrates conductivity and spin-crossover (SCO) transition associated with Fe(II) complex cation subsystem. It was synthesized and structurally characterized at temperatures 100, 300, 400, and 450 K. The compound demonstrates unusual for 7,7,8,8,-tetracyanoquinodimethane (TCNQ)-based salts quasi-two-dimensional conductivity. Pronounced changes of the in-plane direct-current resistivity and intensity of the electron paramagnetic resonance (EPR) signal, originated from TCNQ subsystem, precede the SCO transition at the midpoint T* = 445 K. The boltzmannian growth of the total magnetic response and structural changes in the vicinity of T* uniquely show that half [Fe{HC(pz)3}2] cations exist in high-spin state. Robust broadening of the EPR signal triggered by the SCO transition is interpreted in terms of cross relaxation between the TCNQ and Fe(II) spin subsystems.

Influence of Halogen Atoms on Spin‐Crossover Properties of 1,2,4‐Triazole‐Based 1D Iron(II) Polymers

AbstractThe introduce of halogen atoms (F, Cl, Br, I) to the triazole‐based ligand N‐benzyl‐4‐amino‐1, 2, 4‐triazole (L) have shown a significant effect on the spin‐crossover (SCO) properties of the corresponding one‐dimensional (1D) coordination Fe (II) polymers with chemical formula [Fe(4‐X–L)3](BF4)2 (X=F, Cl, Br, and I). Compared with the [FeL3](BF4)2, the electronegative halogen atoms have increased the π‐acceptor character of these ligands, which thus improved the ligand field strength and induced the occurrence of SCO for the Fe (II) polymers at higher temperatures. The SCO transition temperatures T1/2 have changed from 200 K to 249 (I), 250 (Br), 252 (Cl) and 275 (F) K, respectively. More importantly, the UV‐Vis absorption spectrum and density functional theory (DFT) calculations indicated that the transition temperatures and the width of thermal hysteresis loops have shown a positive correlation with the electronegativity of the halogen atoms.