Spin-crossover Molecules Research Articles

Anomalous Light-Induced Spin-State Switching for Iron(II) Spin-Crossover Molecules in Direct Contact with Metal Surfaces.

Light-induced spin-state switching is one of the most attractive properties of spin-crossover materials. In bulk, low-spin (LS) to high-spin (HS) conversion via the light-induced excited spin-state trapping (LIESST) effect may be achieved with a visible light, while the HS-to-LS one (reverse-LIESST) requires an excitation in the near-infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for FeII spin-crossover molecules that are in direct contact with metallic (111) single-crystal surfaces (copper, silver, and gold). To interpret this anomalous spin-state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin-state switching at the molecule-metal interface.

Multilevel Resistance Switching and Enhanced Spin Transition Temperature in Single- and Double-Molecule Spin Crossover Nanogap Devices

Spin crossover (SCO) molecules are promising bi-stable magnetic switches with applications in molecular spintronics. However, little is known about the switching effects of a single SCO molecule when it is confined between two metal electrodes. Here we examine the switching properties of a [Fe(III)(EtOSalPet )(NCS)] SCO molecule that is specifically tailored for surface deposition and binding to only one gold electrode in a nanogap device. Temperature dependent conductivity measurements on SCO molecule containing electromigrated gold break junctions show voltage independent telegraphic-like switching between two resistance states at temperature below 200 K. The transition temperature is very different from the transition temperature of 83 K that occurs in a bulk film of the same material. This indicates that the bulk, co-operative SCO phenomenon is no longer preserved for a single molecule and that the surface interaction drastically increases the temperature of the SCO phenomenon. Another key finding of this work is that some devices show switching between multiple resistance levels. We propose that in this case, two SCO molecules are present within the nanogap with both participating in the electronic transport and switching.

Properties of 2D hexagonal spin-crossover nanosystem: a Monte Carlo study

The behavior of thermal hysteresis of 2-D hexagonal spin-crossover nanosystem was studied on the basis of microscopic approach, using an Ising-like model. The results were obtained using Monte Carlo method based on the Metropolis algorithm. In the framework of the considered model, a relation between the system size and interaction strength of the neighbor spin-crossover molecules was established. By applying external pressure, a narrowing of the system’s hysteresis and a shift of the transition curves toward higher temperature were observed. The application of pressure also leads to a switching between the HS and LS states of the system, which makes such system promising and desirable in sensor applications (as pressure sensors). The influence of the defects on the system transition curves was investigated. Presence of which leads to the narrowing of the hysteresis width. The obtained results of numerical simulations are in accordance with available theoretical and experimental ones of other authors.

A molecular spin-crossover film allows for wavelength tuning of the resonance of a Fabry–Perot cavity

A wavelength-tunable optical cavity was constructed using spin crossover molecules.

Synchrotron-based Mössbauer spectroscopy characterization of sublimated spin crossover molecules.

The spin crossover (SCO) efficiency of [57Fe(bpz)2(phen)] (where bpz = bis(pyrazol-1-yl)borohydride and phen = 9,10-phenantroline) molecules deposited on gold substrates was investigated by means of synchrotron Mössbauer spectroscopy. The spin transition was driven thermally, or light induced via the LIESST (light induced excited spin-state trapping) effect. Both sets of measurements show that, once deposited on a gold substrate, the efficiency of the SCO mechanism is modified with respect to molecules in the bulk phase. A correlation in the distribution of hyperfine parameters in the sublimated films, not evidenced so far in the bulk phase, is reported. This translates into geometrical distortions of the first coordination sphere of the iron atom that seem to correlate with the decreased spin conversion. The work reported clearly shows the potentiality of synchrotron Mössbauer spectroscopy for the characterization of nanostructured Fe-based SCO systems, thus resulting as a key tool in view of their applications in innovative nanoscale devices.

Effect of ligand methylation on the spin-switching properties of surface-supported spin-crossover molecules

X-ray absorption spectroscopy investigations of the spin-state switching of spin-crossover (SCO) complexes adsorbed on a highly-oriented pyrolytic graphite (HOPG) surface have shown so far that HOPG is a promising candidate to realize applications such as spintronic devices because of the stability of SCO complexes on HOPG and the possibility of highly efficient thermal and light-induced spin-state switching. Herein, we present the spin switching of several Fe(II) SCO complexes adsorbed on an HOPG surface with particular emphasis on the thermally induced spin transition behaviour with respect to different structural modifications. The complexes of the type [Fe(bpz)2(L)] (bpz = dihydrobis(pyrazolyl)borate, L = 1,10-phenanthroline, 2,2′-bipyridine) and their methylated derivatives exhibit SCO in the solid state with some differences regarding cooperative effects. However, in the vacuum-deposited thick films on quartz, complete and more gradual spin transition behavior is observable via UV/vis spectroscopy. In contrast to that, all complexes show large differences upon direct contact with HOPG. Whereas the unmodified complexes show thermal and light-induced SCO, the addition of e.g. two or four methyl groups leads to a partial or a complete loss of the SCO on the surface. The angle-dependent measurement of the N K-edge compared to calculations indicates that the complete SCO and HS-locked molecules on the surface exhibit a similar preferential orientation, whereas complexes undergoing an incomplete SCO exhibit a random orientation on the surface. These results are discussed in the light of molecule-substrate interactions.

Importance of Epitaxial Strain at a Spin-Crossover Molecule-Metal Interface.

Spin-crossover molecules are very appealing for use in multifunctional spintronic devices because of their ability to switch between high-spin and low-spin states with external stimuli such as voltage and light. In actual devices, the molecules are deposited on a substrate, which can modify their properties. However, surprisingly little is known about such molecule-substrate effects. Here we show for the first time, by grazing incidence X-ray diffraction, that an FeII spin-crossover molecular layer displays a well-defined epitaxial relationship with a metal substrate. Then we show, by both density functional calculations and a mechanoelastic model, that the resulting epitaxial strain and the related internal pressure can induce a partial spin conversion at low temperatures, which has indeed been observed experimentally. Our results emphasize the importance of substrate-induced spin state transitions and raise the possibility of exploiting them.

Computational Modeling of Transition Temperatures in Spin-Crossover Systems

A survey of different computational approaches to compute thermochemical properties and, in particular, transition temperatures (T1/2) in spin-crossover (SCO) systems are presented. Asides from the possibility of computing accurate values, this work centers its efforts in the use of computational tools to explain trends in different families of SCO molecules. Understanding the impact that chemical modifications (both electronic and steric) have over the ligand-field around the metal center is key in rationalizing the observed trends in T1/2. By using concepts from molecular orbital theory combined with the results from the calculations, a simple yet, accurate depiction of the shift in T1/2 can be outlined. Therefore, the presented results allow for a rational design of new SCO systems with tailored properties.

Ferroelectric metallomesogens composed of achiral spin crossover molecules.

Ferroelectric liquid crystals (FLCs) are fascinating functional materials that have a remnant and electrically invertible polarization. To date, typical FLCs have been mainly realized by molecular design such as the incorporation of chirality into a given molecular structure. Here, we report for the first time ferroelectricity induced by spin transition associated with a crystal - liquid crystal phase transition in achiral molecules. Iron(ii) metallomesogens incorporating alkyl chains of type [Fe(3C n -bzimpy)2](BF4)2 (n = 8 (1), 10 (2), 12 (3), 14 (4), 16 (5) and 18 (6); bzimpy = 2,6-bis(benzimidazol-2'-yl)pyridine) that exhibit spin crossover (SCO) phenomena have been synthesized. Compounds 5 and 6 were each demonstrated to show SCO behaviour along with the occurrence of a phase transition between the crystalline (Cr) state and corresponding chiral smectic C (SmC*) state. The distortion of the coordination sphere in the high spin state is seen to trigger the generation of the SmC* state. The liquid crystalline compounds do not display ferroelectric behaviour in their Cr state but do exhibit ferroelectric hysteresis loops in their SmC* state. Ferroelectric switching was clearly confirmed by second harmonic generation (SHG) experiments involving the respective phases. These findings will undoubtedly lead to new strategies for the design of new FLCs based on metal-centred spin transitions.

Thermodynamical aspects of the spin crossover phenomenon

Abstract Fundamental aspects of spin crossover (SCO) mechanisms are reviewed through considerations of ligand/crystal field theory, thermodynamics, and modeling of the thermoinduced spin transition in the solid state based on macroscopic–mesoscopic approaches . In particular, we highlight success of thermodynamic models in the simulation of first-order spin transitions with hysteretic behaviors (bistability) and multistep conversions. Bistability properties originate from elastic interactions, the so-called cooperativity between SCO molecules in the crystal packing. Although physical and chemical properties and thermodynamical quantities of noninteracting SCO compounds can be readily injected in macroscopic models, taking cooperativity into account remains problematic. The relationship between phenomenological numerical parameters and experimentally accessible quantities can only be most of the time indirectly established. Recent extensions of these thermodynamical models to grasp SCO properties at the nanoscale and combinations with ab initio numerical methods show that macroscopic models still constitute useful theoretical tools to investigate SCO phenomena. The necessity to further probe the thermomechanical properties of SCO materials is also emphasized.

Benchmarking Density Functional Methods for Calculation of State Energies of First Row Spin-Crossover Molecules.

A systematic study of the performance of several density functional methodologies to study spin-crossover (SCO) on first row transition metal complexes is reported. All functionals have been tested against several mononuclear systems containing first row transition metal complexes and exhibiting spin-crossover. Among the tested functionals, the hybrid meta-GGA functional TPSSh with a triple-ζ basis set including polarization functions on all atoms provides the best results across different metals and oxidation states, and its performance in both predicting the correct ground state and the right energy window for SCO to occur is quite satisfactory. The effect of some additional contributions, such as zero-point energies, relativistic effects, and intramolecular dispersion interactions, has been analyzed. The reported strategy thus expands the use of the TPSSh functional to other metals and oxidation states other than FeII, making it the method of choice to study SCO in first row transition metal complexes. Additionally, the presented results validate the potential use of the TPSSh functional for virtual screening of new molecules with SCO, or its use in the study of the electronic structure of such systems.

Linking Electronic Transport through a Spin Crossover Thin Film to the Molecular Spin State Using X-ray Absorption Spectroscopy Operando Techniques

One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. Although this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's [Fe(H2B(pz)2)2(NH2-phen)] molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds.

Evolution of cooperativity in the spin transition of an iron(II) complex on a graphite surface

Cooperative effects determine the spin-state bistability of spin-crossover molecules (SCMs). Herein, the ultimate scale limit at which cooperative spin switching becomes effective is investigated in a complex [Fe(H2B(pz)2)2(bipy)] deposited on a highly oriented pyrolytic graphite surface, using x-ray absorption spectroscopy. This system exhibits a complete thermal- and light-induced spin transition at thicknesses ranging from submonolayers to multilayers. On increasing the coverage from 0.35(4) to 10(1) monolayers, the width of the temperature-induced spin transition curve narrows significantly, evidencing the buildup of cooperative effects. While the molecules at the submonolayers exhibit an apparent anticooperative behavior, the multilayers starting from a double-layer exhibit a distinctly cooperative spin switching, with a free-molecule-like behavior indicated at around a monolayer. These observations will serve as useful guidelines in designing SCM-based devices.

Thermoelectronic transport through spin-crossover single molecule Fe[(H2Bpz2)2bipy

By means of density functional theory combined with the method of Keldysh nonequilibrium Green’s function, the thermal transport properties of high- and low-spin states of mononuclear FeII molecules with spin-crossover characteristics are studied. It is found that the high-spin molecular junction has a larger current than the low-spin one, producing thermally-induced switching effect. Furthermore, for high spin state molecule, the spin-up thermo-current is strongly blocked, thus achieving a pure thermo spin current. The enhanced Seebeck coefficient and the figure of merit value of high-spin state indicate that it is an ideal candidate for thermoelectric applications.

The Electronic Structure Signature of the Spin Cross-Over Transition of [Co(dpzca)2

Abstract The unoccupied electronic structure of the spin crossover molecule cobalt (II) N-(2-pyrazylcarbonyl)-2-pyrazinecarboxamide, [Co(dpzca)2] was investigated, using X-ray absorption spectroscopy (XAS) and compared with magnetometry (SQUID) measurements. The temperature dependence of the XAS and molecular magnetic susceptibility χmT are in general agreement for [Co(dpzca)2], and consistent with density functional theory (DFT). This agreement of magnetic susceptibility and X-ray absorption spectroscopy provides strong evidence that the changes in magnetic moment can be ascribed to changes in electronic structure. Calculations show the choice of Coulomb correlation energy U has a profound effect on the electronic structure of the low spin state, but has little influence on the electronic structure of the high spin state. In the temperature dependence of the XAS, there is also evidence of an X-ray induced excited state trapping for [Co(dpzca)2] at 15 K.

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.

Numerical Investigations of the Thermal, Pressure and Size Effects on 2D Spin Crossover Nanoparticles

In the framework of the Ising-like model, the thermal and pressure effects on the spin crossover systems are evaluated through two-states fictitious spin operators σ with eigenvalues \U0001d70e = −1 and \U0001d70e = +1 respectively associated with the low-spin (LS) and highspin (HS) states of each spin-crossover (SCO) molecule. Based on each configurational state, the macroscopic SCO system, is described by the following variables: m=Σ σi, s=Σ σi σj and c=Σ σk standing respectively for the total magnetization, the short-range correlations and surface magnetization. To solve this problem, we first determine the density of macrostates d[m][s][c], giving the number of microscopic configurations with the same m, s and c values. In this contribution, two different ways have been performed to calculate this important quantity: (i) the entropic sampling method, based on Monte Carlo simulations and (ii) a new algorithm based on specific dynamic programming. These two methods were tested on the 2D SCO nanoparticles for which, we calculated the average magnetization < σ> taking into account for short-, long-range interactions as well as for the interaction between surface molecules with their surrounding matrix. We monitored the effect of the pressure, temperature and size on the properties of the SCO nanoparticles.

Robust and Selective Switching of an FeIII Spin-Crossover Compound on Cu2N/Cu(100) with Memristance Behavior.

The switching between two spin states makes spin-crossover molecules on surfaces very attractive for potential applications in molecular spintronics. Using scanning tunneling microscopy, the successful deposition of [Fe(pap)2]+ (pap = N-2-pyridylmethylidene-2-hydroxyphenylaminato) molecules on Cu2N/Cu(100) surface is evidenced. The deposited FeIII spin-crossover compound is controllably switched between three different states, each of them exhibiting a characteristic tunneling conductance. The conductance is therefore employed to readily read the state of the molecules. A comparison of the experimental data with the results of density functional theory calculations reveals that all Fe(pap)2 molecules are initially in their high-spin state. The two other states are compatible with the low-spin state of the molecule but differ with respect to their coupling to the substrate. As a proof of concept, the reversible and selective nature of the switching is used to build a two-molecule memory.

Soft-x-ray-induced spin-state switching of an adsorbed Fe(II) spin-crossover complex

For probing the nature of spin-state switching in spin-crossover molecules adsorbed on surfaces, x-ray absorption spectroscopy has emerged as a powerful tool due to its high sensitivity and element selectivity in tracing even subtle electronic, magnetic, or chemical changes. However, the x-rays itself can induce a spin transition and might have unwanted influence while investigating the effect of other stimuli such as temperature or light, or of the surface, on the spin switching behaviour. Herein, we present the spin switching of an Fe(II) complex adsorbed on a highly oriented pyrolytic graphite surface with particular emphasis on the x-ray-induced switching. For a submonolayer coverage, the complex undergoes a complete and reversible temperature- and light-induced spin transition. The spin states are switched both ways by x-rays at 5 K, i.e. from the high-spin state to the low-spin state or vice versa, depending on the relative amount of each species. Furthermore, we quantify the fraction of molecules undergoing soft x-ray-induced photochemistry, a process which results in an irreversible low-spin state component, for a particular exposure time. This can be greatly suppressed by reducing the beam intensity.

Frontispiece: A Bistable Microelectromechanical System Actuated by Spin‐Crossover Molecules

Frontispiece: A Bistable Microelectromechanical System Actuated by Spin‐Crossover Molecules