Spin Transition Phenomenon Research Articles

Bistable Spin-Crossover Nanoparticles for Molecular Electronics.

The field of spin-crossover complexes is rapidly evolving from the study of the spin transition phenomenon to its exploitation in molecular electronics. Such spin transition is gradual in a single-molecule, while in bulk it can be abrupt, showing sometimes thermal hysteresis and thus a memory effect. A convenient way to keep this bistability while reducing the size of the spin-crossover material is to process it as nanoparticles (NPs). Here, the most recent advances in the chemical design of these NPs and their integration into electronic devices, paying particular attention to optimizing the switching ratio are reviewed. Then, integrating spin-crossover NPs over 2D materials is focused to improve the endurance, performance, and detection of the spin state in these hybrid devices.

Pressure-Induced Mixed States Caused by Spin-Elastic Interactions during First-Order Spin Phase Transition in Spin Crossover Compounds.

Recently, the possibility of exploiting the phenomenon of spin transition (ST) has been intensively investigated; therefore, it is particularly important to study the behavior of ST under various stimuli. Here, the shape and content of the intermediate phase of ST in Hoffmann-like compounds [Fe(Fpz)2M(CN)4] (M = Pt, Pd) under external stimuli are studied. For this purpose, magnetic and Raman spectroscopy studies were carried out. In pressure-induced spin transition (PIST), a mixture of high-spin and low-spin states appears, while in temperature-induced spin transition (TIST), a homogeneous state occurs. The first-order ST induced by pressure has a hysteresis but is not abrupt. However, the temperature-induced spin transition at ambient pressure is hysteretic and abrupt. To investigate this difference, we discuss using a thermodynamic model that considers elastic interactions, showing that the slope of the hysteresis loop is related to the appearance of internal pressure, which is related to the difference in sample compressibility under high-spin and low-spin states.

Elastic Modeling of Two-Step Transitions in Sterically Frustrated 1D Binuclear Spin-Crossover Chains

Among the large family of spin-crossover materials, binuclear systems play an important role due to their specific molecular configurations, allowing the presence of multi-step transitions and elastic frustration. Although this issue benefited from a significant number of spin-based theories, there is almost no elastic description of the spin transition phenomenon in binuclear systems. To overcome this deficiency, in this work we develop the first elastic modeling of thermal properties of binuclear spin-crossover solids. At this end, we investigated a finite spin-crossover open chain constituted of elastically coupled binuclear (A = B) blocks, ⋯A=B−A=B−A=B⋯, in which the considered equivalent A and B sites may occupy two configurations, namely low-spin (LS) and high-spin (HS) states. The sites of the binuclear unit interact via an intramolecular spring and couple to the neighboring binuclear units via other springs. The model also includes the change of length inside and between the binuclear units subsequent to the spin state changes. When injecting an elastic frustration inside the binuclear unit in the LS state, competing interactions between the intra- and the inter-binuclear couplings emerge. The latter shows that according to the intra- and inter-binuclear elastic constants and the strength of the frustration, multi-step transitions are derived, for which a specific self-organization of type (HS = HS)-(LS-LS)-(HS = HS)⋯ is revealed and discussed. Finally, we have also studied the relaxation of the metastable photoinduced HS states at low temperature, in which two relaxation regimes with transient self-organized states were identified when monitoring the elastic frustration rate or the ratio of intra- and intermolecular elastic interactions. These behaviors are reminiscent of the thermal dependence of the order parameters of the system. The present model opens several possibilities of extensions of elastic frustrations acting in polynuclear spin-crossover systems, which may lead to other types of spin-state self-organizations and relaxation dynamics.

Kompleks Besi(II) dengan ligan 3-bpp: review

The change of two different spin electronic states under the influence of temperature, pressure and light irradiation is known as the Spin Transition or Spin Crossover (SCO) phenomenon.  Spin transition exists on octahedral complexes with an intermediate ligand field, one of the ligands is 2,6-bis (pyrazol-3-yl)pyridine or 3-bpp. Spin transition complexes were intensively investigated because they are highly potential candidates for electronic materials, such as sensors, molecular switches and information storages.  The iron(II) complex with 3-bpp ligand has shown SCO characteristics including different transition pattern and transition temperature which were influenced by type of the counter anions.  The iron(II) complexes with different types of counter anions have exhibited SCO phenomenon, due to the effect of temperature with abrupt transition.  However, the presence of hydrate water in the iron(II) complex results in the higher temperature transition.  In addition of that, the transition pattern has changed from the abrupt transition into the gradual transition types.  Several studies of SCO properties of the complex Fe(II)-3-bpp reported that the transition type and the temperature transition were influenced by the type of counter anion and the amount of hydrate molecules.  With various transition patterns and transition temperatures, the potential of Fe(II)-bpp complexes as SCO materials is more interesting to explored.   Keywords: Iron(II) Complex, 3-bpp Ligand, Spin Crossover

Magnetic-field induced multi-step transitions in ferromagnetic spin-crossover solids within the BEG model

We study by means of the 2D Blume–Emery–Griffiths (BEG) spin-1 model, spin-crossover (SCO) and prussian blue analogs (PBAs) solids. In this model, the spin states, which can be high-spin (HS) or low-spin (LS), interact magnetically and elastically with their nearest neighbors. To account for the volume change, accompanying the spin transition phenomenon, all interactions through the lattice are assumed as temperature-dependent. In addition, the system is subject to a variable magnetic field lifting the degeneracy in the HS state. A stochastic cooperative dynamics of this BEG-like Hamiltonian, describing the equilibrium and nonequilibrium properties of ferromagnetic spin-crossover solids, is derived from the Glauber approach, with appropriate Arrhenius microscopic transition rates. The model generates under the magnetic field, sigmoidal relaxation and a hysteresis phenomenon of the HS fraction, as well as multistep behavior of the magnetization. These behaviors open the way to new route of multi-stable systems, desired in multi-byte electronics.

The average value of the spin squared operator as an order parameter for spin phase transitions without spontaneous lowering of symmetry

Phase transitions from the low-spin to the high-spin state are a unique physical phenomenon without lowering of symmetry. In contrast to magnetic phase transitions, for which vector or tensor of physical quantities are used as order parameters, we have shown that for spin phase transitions the order parameter is a scalar quantity—the thermodynamic mean of spin square operator, which was not previously used at all in the theory of phase transitions. The free energy in the form of a functional of this order parameter is determined, and the phase diagrams for spin transitions are constructed. The influence of the pressure on spin transition is analyzed also. It is shown that the spin Hamiltonian with this order parameter allows one to obtain all possible spin transformations in compounds. At the same time, this order parameter correctly reflects the physical nature of the spin transition phenomena.

Magnetic phase diagram of CrPS4 and its exchange interaction in contact with NiFe

The magnetic phase diagram of the two-dimensional van der Waals magnet CrPS4 and the exchange bias effect of CrPS4 in contact with NiFe film have been investigated. Based on the magnetic measurements, we figure out the relatively low spin-flop field and spin-flip field for CrPS4, both of the spin transition phenomena are strongly affected by the temperature. The perpendicular exchange bias effect is studied in CrPS4 single-crystal flake covered with 5 nm NiFe. Meanwhile, the variation of the cooling field has a great influence on the exchange bias field and coercivity, which is mainly attributed to the competition between the Zeeman energy and the exchange coupling at the interface as well as the formation of the multi-domain state.

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two-Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure.

A two-step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3-CNpy)2 ][Re(CN)8 ]}⋅H2 O (1) (3-CNpy=3-cyanopyridine) assembly consisting of cyanido-bridged FeII -ReV square grid sheets bonded by Cs+ ions. The presence of two non-equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non-covalent interlayer interactions involving Cs+ , [ReV (CN)8 ]3- ions, and 3-CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin-transition phenomenon could be tuned by an external pressure giving the room-temperature range of SCO, as well as by visible-light irradiation, inducing an efficient recovery of the high-spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

Thermo-Reversible Hybrid Gels Formed from the Combination of Isotactic Polystyrene and [Fe(II) (4-Octadecyl-1,2,4-Triazole)3(ClO4)2]n Metallo-Organic Polymer: Thermal and Viscoelastic Properties.

Nano-sized one-dimensional metallo-organic polymers, characterized by the phenomenon of spin transition, are excellent candidates for advanced technological applications such as optical sensors, storage, and information processing devices. However, the main drawback of this type of polymers is their fragile mechanical properties, which hinders its processing and handling, and makes their practical use unfeasible. To overcome this problem, in this work, hybrid thermo-reversible gels are synthesized by combination of a metallo-organic polymer and isotactic polystyrene (iPS) in cis-decaline. A detailed investigation of the thermal and viscoelastic properties of the hybrid gels, in terms of iPS and metallo-organic polymer concentration is performed by means of differential scanning calorimetry and oscillatory rheology, respectively. From the analysis of the thermal properties, three transitions have been determined upon heating: Monotectic transition of the iPS gel, melting of the iPS gel, and melting of the metal-organic polymer gel, which suggest that the gels of the two polymers are formed independently in the hybrid gel, as long as the two polymers are in concentrations above the corresponding critical gelation concentrations. Results regarding viscoelastic properties and morphology confirmed that hybrid gels consisted of an interpenetrated network of polymer gels, formed by iPS and metallo-organic poymer gels growing independently.

Moving Molecules in Crystalline Solids: Gradual Structure Transition and Spin Transition/Crossover

Magnetic switches working in solid states are of recent interest for applications to sensor, memory, etc. The author and co-workers have developed various unconventional spin transition/crossover materials. The first example is a supramolecular chemistry consisting of genuine organic nitroxide biradicals with a triplet ground state. Each nitroxide group is located close to each other to form weak covalent bonds in an intermolecular fashion. Biradicals are polymerized/depolymerized stepwise. The second example belongs to 3d-2p heterospin systems where the nitroxide oxygen atom is directly bonded to a nickel(II) or copper(II) ion. The planar/nonplanar chelate structure changes, accompanied by high-/low-spin transition due to a 3d-2p exchange-coupling switch. A novel entropy-driven spin crossover scenario has been established. The third example is a 3d iron(II) spin crossover material carrying a stearyl (C18) group. An order-disorder-type structural transition appears with respect to the alkyl conformation. As these examples show, single-crystal-to-single-crystal structural transitions are often observed. It is because the spin entropy term regulates the atomic dislocation enthalpy, and the entropy change due to the spin multiplicity is basically small. These molecular motions clarified by means of detailed crystallography afford one of the most convincing evidence for the spin transition phenomenon.

Direct Observation of Charge Transfer and Magnetism in Fe4Co4 Cyanide-Bridged Molecular Cubes.

We have studied the zero-dimensional cubane molecular correspondent of a Prussian blue analogue Cs-Fe4Co4 at low temperature and high magnetic field by means of L-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We probe the magnetic and electronic structures of Fe and Co separately upon light irradiation, which allows us to observe directly the electron transfer coupled to a spin transition phenomenon within the molecular cubes and to investigate the nature of the metastable photoexcited state. The magnetic moments in the photoexcited state are found to be M = 1.3μB ( Mspin = 0.59μB with large orbital moment, Morbit = 0.74μB) for low-spin FeIII and M = 1.5μB ( Mspin = 1.08μB with orbital moment, Morbit = 0.41μB) for high-spin CoII at 2 K and 6.8 T. From our results, we evidence that a strong antiferromagnetic coupling between the metal ions can be ruled out.

Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone).

Two new iron(II) neutral complexes of bis(1-methylimidazol-2-yl)ketone (Mebik) with molecular formula [FeII(Mebik)2(NCS)2] (1) and [FeII(Mebik)2(NCSe)2] (2) have been synthesized and characterized by magnetic measurements, single-crystal X-ray diffraction, and solid state UV-vis spectroscopy. The temperature dependent magnetic susceptibility measurements of crystalline samples of both compound show the occurrence of a gradual spin transition centered at T1/2 = 260 K and 326 K, respectively. The crystal structures of both compounds were determined at different temperatures, below and above the transition, in order to detect the structural changes associated with the spin transition. The main structural modifications, when passing from the low-spin to the high-spin form, consist of an important lengthening of the Fe-N(Mebik) and Fe-N (C-S/Se) distances (by ca. 0.20 and 0.18 Å, respectively) and a noticeable variation of the N-Fe-N angles, leading to a more distorted [Fe-N6] octahedron. The spin-transition phenomenon also affects the optical properties, with significant decrease of the intensity of the Metal-to-Ligand charge transfer band upon increasing the temperature. Finally, both complexes exhibit a light-induced excited spin-state trapping under laser light irradiation at low temperature. DFT calculations were also carried out on these complexes in order to rationalize the theoretically predicted magnetic and optical behavior with those of the experimental one. The results clearly highlights the dramatic alteration of the magneto-structural behavior of the tris-chelate spin-crossover complex upon substituting one Mebik with NCS and NCSe ligands.

Spin-Crossover Iron(II) Coordination Polymer with Fluorescent Properties: Correlation between Emission Properties and Spin State.

A spin-crossover coordination polymer [Fe(L1)(bipy)]n (where L = a N2O22- coordinating Schiff base-like ligand bearing a phenazine fluorophore and bipy = 4,4'-bipyridine) was synthesized and exhibits a 48 K wide thermal hysteresis above room temperature (T1/2↑ = 371 K and T1/2↓ = 323 K) that is stable for several cycles. The spin transition was characterized using magnetic measurements, Mössbauer spectroscopy, and DSC measurements. T-dependent X-ray powder diffraction reveals a structural phase transition coupled with the spin transition phenomenon. The dimeric excerpt {(μ-bipy)[FeL1(MeOH)]2}·2MeOH of the coordination polymer chain crystallizes in the triclinic space group P1̅ and reveals that the packing of the molecules in the crystal is dominated by hydrogen bonds. Investigation of the emission properties of the complexes with regard to temperature shows that the spin crossover can be tracked by monitoring the emission spectra, since the emission color changes from greenish to a yellow color upon the low spin-to-high spin transition.

Lattice-Solvent Effects in the Spin-Crossover of an Fe(II)-Based Material. The Key Role of Intermolecular Interactions between Solvent Molecules.

The spin transition of Fe(II) complexes is the subject of intensive synthetic and computational efforts. In this manuscript, we analyze the spin crossover (SCO) of [Fe(E-dpsp)2]2+ (1), which features a spin transition depending on the cocrystallizing solvent molecules. Whereas the use of acetone results in a hysteretic spin transition at ∼170 K, the use of propylene carbonate (PC) results in a permanent diamagnetic signal up to 300 K. By means of DFT+U+D2 calculations in the solid state of the material, we unravel the reasons for such different behavior. Our results allow us to ascribe the relatively low transition temperature of 1(BF4)2·acetone to the distorted arrangement of the SCO molecules in the low-spin state of the material. In turn, intermolecular interactions play the primary role in the case of 1(BF4)2·2PC. In particular, we found that solvent-solvent interactions actively promote the stability of the low-spin state due to the formation of PC dimers. These dimers would appear at larger distances in the high-spin phase, with the subsequent loss of phase stability. This is yet another proof of how subtle is the spin transition phenomenon in Fe(II)-based architectures.

Investigation of surface energies in spin crossover nanomaterials: the role of surface relaxations.

We analyse in detail the role of surface relaxations on the spin transition phenomenon through an Ising-like model solved in the inhomogeneous mean field approach. We show the surface relaxation tends to decrease the energy cost of missing bonds. Cooperative phenomena are also affected, leading to an asymmetric hysteresis loop. The underlying mechanisms are investigated by calculating thermodynamics excess quantities. Far from the spin transition, the contribution of surface relaxations to the excess internal energy, entropy and free energy is negligible, but their role becomes substantial around the transition temperature.

Room-Temperature Spin-Transition Iron Compounds

Spin transition complexes are an interesting class of materials exhibiting molecular bistability with potential applications in nanotechnological devices as memory storage units, sensors or displays. Since the discovery of the spin transition phenomenon in tris(N,Ndialkyldithiocarbamato) iron(III) complexes, numerous investigations have been devoted to this field of molecular magnetism. The spin transition phenomenon is probably the most spectacular example of bistability in molecular chemistry. However, it is a challenge to obtain spin transition materials when working under ambient conditions (eg. room temperature and pressure), which would be highly advantageous for potential applications. So far, only some Fe(II) and Fe(III) molecular systems have shown temperature-induced spin transitions around and even above room temperature. Within this review, we discuss the characteristics of this class of bistable compounds in detail and we try to draw more general conclusions regarding the integration, implementation and application of spin transition compounds as switching elements in hybrid molecular devices.

Elastic Frustration Causing Two-Step and Multistep Transitions in Spin-Crossover Solids: Emergence of Complex Antiferroelastic Structures.

Two-step and multistep spin transitions are frequently observed in switchable cooperative molecular solids. They present the advantage to open the way for three- or several-bit electronics. Despite extensive experimental studies, their theoretical description was to date only phenomenological, based on Ising models including competing ferro- and antiferro-magnetic interactions, even though it is recognized that the elastic interactions are at the heart of the spin transition phenomenon, due to the volume change between the low- and high-temperature phases. To remedy this shortcoming, we designed the first consistent elastic model, taking into account both volume change upon spin transition and elastic frustration. This ingredient was revealed to be powerful, since it was able to obtain all observed experimental configurations in a consistent way. Thus, according to the strength of the elastic frustration, the system may undergo first-order transition with hysteresis, gradual, hysteretic two-step or multistep transitions, and incomplete transitions. Furthermore, the analysis of the spatial organization of the HS and LS species in the plateau regions revealed the emergence of complex antiferro-elastic patterns going from simple antiferro-magnetic-like order to long-range spatial modulations of the high-spin fraction. These results enabled us to identify the elastic frustration as the fundamental mechanism at the origin of the very recent experimental observations showing the existence of organized spatial modulations of the high-spin fraction inside the plateau of two-step spin transitions.

Analysis of hysteretic spin transition and size effect in 3D spin crossover compounds investigated by Monte Carlo Entropic sampling technique in the framework of the Ising-type model

In spin crossover (SCO) systems, the shape of the hysteresis curves are closely related to the interactions between the molecules, which these play an important role in the response of the system to an external parameter. The effects of short-range interactions on the different shape of the spin transition phenomena were investigated. In this contribution we solve the corresponding Hamiltonian for a three-dimensional SCO system taking into account short-range and long-range interaction using a biased Monte Carlo entropic sampling technique and a semi-analytical method. We discuss the competition between the two interactions which governs the low spin (LS) - high spin (HS) process for a three-dimensional network and the cooperative effects. We demonstrate a strong correlation between the shape of the transition and the strength of short-range interaction between molecules and we identified the role of the size for SCO systems.

Cellulose fiber nanocomposites displaying spin-crossover properties

Linter cellulose fiber based nanocomposites were prepared by functionalizing the fibers with [Fe(hptrz)3](OTs)2 spin-crossover nanoparticles and acridine orange dye molecules. The composites were characterized by electronic (UV–vis and fluorescence) and vibrational (Raman, FTIR) spectroscopies as well as by electronic and optical microscopies. The cellulose sheets prepared from the nanocomposite show significant thermochromic and thermofluorescent effects associated with the spin transition phenomenon, providing scope for paper thermometry and anti-counterfeit applications.

Syntheses, structures and magnetic properties of a series of iron(II)-triazole crystalline coordination compounds: Solvent effect, different substituted groups and incomplete spin transition

Abstract Based on 4-substituted mono- and bis-triazole ligands 4-2-pyridyl-1,2,4-triazole (L1) and 2,6-(1,2,4-triazole-4-yl)-pyridine (L2), a series of iron(II)-triazole complexes, namely [Fe2(μ2-L1)3(L1)2(NCS)4] 2H2O (1), [Fe2(μ2-L1)3(L1)2(NCS)4] CH3OH CH3CH2OH (2) and [Fe(μ2-L2)2(NCS)2]n (3) have been isolated. For the Fe(II)-L1 system, though dinuclear complexes were obtained in both aqueous solution and methanol/ethanol solution for 1 and 2, respectively, anti-ferromagnetic interactions were found in 1 while incomplete spin transition phenomenon was found in 2. Low temperature structural analysis (100 K) of 2 is consistent with one of the Fe(II) centers within the dinuclear complex at low spin (LS) state and the other at high-spin (HS) state resulting in a [LS:HS] species. When L2 is used under the similar preparation method for 1–2, one-dimensional neutral iron (II) chain complex 3 is isolated. The different substituted groups and solvent effect are both important for self-assembly and different magnetic properties of these crystalline iron(II)-triazole complexes 1–3.