Spin Crossover Complexes Research Articles

Controlling Spin Switching with Anionic Supramolecular Frameworks

Encasing the classic spin-crossover (SCO) complex cation [Co(terpy)2]2+ in different anionic supramolecular frameworks modulates its SCO behavior, tuning both its T1/2 (shift of up to 200 K) and th...

Resistance switching in large-area vertical junctions of the molecular spin crossover complex [Fe(HB(tz)3)2]: ON/OFF ratios and device stability

Multilayer crossbar junctions composed of ITO/[Fe(HB(1,2,4-triazol-1-yl)3)2]/M (with M = Al or Ca) were fabricated and investigated for their resistance switching properties. Current–voltage–temperature maps revealed ON/OFF resistance ratios as high as 400, with the ON and OFF states defined, respectively, as the low-resistance, low spin state and the high-resistance, high spin state of the spin crossover layer. Similar results were obtained with Al and Ca cathodes indicating that the charge transport in the insulating spin crossover film is at the origin of the resistance switching instead of electron injection at the electrodes. The reproducibility and stability of the device properties were also studied.

Switchable compound for safer explosives

Bomb-detonator materials must strike a balance between maintaining stability and triggering spectacular self-destruction. Chemists now report a material with a fully reversible switching mechanism that could offer more control over initiating an explosion and might be used to build safer detonation devices (J. Am Chem. Soc. 2020, DOI: 10.1021/jacs.9b13835). Thuy-Ai D. Nguyen of Los Alamos National Laboratory and colleagues synthesized a spin-crossover complex called [Fe(Htrz)3]n[ClO4]2n, in which iron is nestled between energetic nitrogen-rich rings common to explosives and an oxidizing counterion of perchlorate, a typical component of fireworks. This complex changes from a low-spin to a high-spin electronic state in response to increased temperature. To test the impact sensitivity of the material, the researchers dropped weights on it inside an anvil cell at various temperatures. They found that the complex exploded under less force in the high-spin state, at 60 °C, compared with the low-spin state, at 2...

First Cobalt(II) Spin Crossover Compound with N4S2-Donorset.

Herein we report the synthesis and characterization of a novel bis-tridentate 1,3,4-thiadiazole ligand (L = 2,5-bis[(2-pyridylmethyl)thio]methyl-1,3,4-thiadiazole). Two new mononuclear complexes of the type [MII(L)2](ClO4)2 (with M = FeII (C1) and CoII (C2)) have been synthesized, containing the new ligand (L). In both complexes the metal centers are coordinated by an N4S2-donorset and each of the two ligands is donating to the metal ion with just one of the tridentate pockets. The iron(II) complex (C1) is in the low spin [LS] state below room temperature and shows an increase in the magnetic moment only above 300 K. In contrast, the cobalt(II) complex (C2) shows a gradual spin crossover (SCO) with T1/2 = 175 K. To our knowledge, this is the first cobalt(II) SCO complex with an N4S2-coordination.

Correlating Mechanical Sensitivity with Spin Transition in the Explosive Spin Crossover Complex [Fe(Htrz)3]n[ClO4]2n.

Spin crossover complexes are known to undergo bond length, volume, and enthalpy changes during spin transition. In an explosive spin crossover complex, these changes could affect the mechanical and initiation sensitivity of the explosive and lead to the development of a new class of sensitivity switchable materials. To explore this relationship, the well-known spin crossover compound [Fe(Htrz)3]n[ClO4]2n (1) was re-evaluated for its explosive properties, and its mechanical impact sensitivity was correlated to spin transition. A variable temperature impact test was developed and used to evaluate the impact sensitivity of 1 in the low spin (LS, S = 0), thermally accessed high spin (HS, S = 2), and mixed LS and HS states. For comparison, the structurally similar Ni compound, [Ni(Htrz)3]n[ClO4]2n (2), which does not undergo a spin transition at accessible temperatures, was synthesized and characterized, and its explosive properties and variable temperature impact sensitivity measured. These results reveal a correlation between impact sensitivity and spin transition, where 1 exhibits lower impact sensitivity in the LS state and increases in sensitivity upon transition to the HS state. Density functional theory was used to predict structural changes that occur upon spin transition that correlate to the change in sensitivity. This demonstrates, for the first time, an explosive spin crossover compound (ExSCO) that exhibits switchable impact sensitivity with a fully reversible internal switching mechanism.

Spin Transition of an Iron(II) Organoborate Complex in Different Polymorphs and in Vacuum-Deposited Thin Films: Influence of Cooperativity.

Two polymorphic modifications (1-I and 1-II) of the new spin crossover (SCO) complex [Fe{H2B(pz)(pypz)}2] (pz = pyrazole, pypz = pyridylpyrazole; 1) were prepared and investigated by differential scanning calorimetry (DSC), magnetic measurements, Mößbauer, vibrational, and absorption spectroscopy as well as single-crystal and X-ray powder diffraction. DSC measurements reveal that upon heating the thermodynamically metastable form 1-II to ∼178 °C it transforms into 1-I in an exothermic reaction, which proves that these modifications are related by monotropism. Both forms show thermal SCO with T1/2 values of 390 K (1-II) and 270 K (1-I). An analysis of the crystal structures of 1-II and the corresponding Zn(II) (2) and Co(II) (3) complexes that are isotypic with 1-I reveals that form II consists of dimers coupled by strong intramolecular π···π interactions, which is not the case for 1-I. In agreement with these findings, investigations of thin films of 1, where significant π···π interactions should be absent, reveal SCO behavior similar to that of 1-I. These results underscore the importance of cooperativity for the spin-transition behavior of this class of complexes.

Contactless Spin Switch Sensing by Chemo-Electric Gating of Graphene.

Direct electrical probing of molecular materials is often impaired by their insulating nature. Here, graphene is interfaced with single crystals of a molecular spin crossover complex, [Fe(bapbpy)(NCS)2 ], to electrically detect phase transitions in the molecular crystal through the variation of graphene resistance. Contactless sensing is achieved by separating the crystal from graphene with an insulating polymer spacer. Next to mechanical effects, which influence the conductivity of the graphene sheet but can be minimized by using a thicker spacer, a Dirac point shift in graphene is observed experimentally upon spin crossover. As confirmed by computational modeling, this Dirac point shift is due to the phase-dependent electrostatic potential generated by the crystal inside the graphene sheet. This effect, named as chemo-electric gating, suggests that molecular materials may serve as substrates for designing graphene-based electronic devices. Chemo-electric gating, thus, opens up new possibilities to electrically probe chemical and physical processes in molecular materials in a contactless fashion, from a large distance, which can enhance their use in technological applications, for example, as sensors.

Iron(II) Spin Crossover Complexes with 4,4'-Dipyridylethyne-Crystal Structures and Spin Crossover with Hysteresis.

Three new iron(II) 1D coordination polymers with cooperative spin crossover behavior showing thermal hysteresis loops were synthesized using N2O2 Schiff base-like equatorial ligands and 4,4′-dipyridylethyne as a bridging, rigid axial linker. One of those iron(II) 1D coordination polymers showed a 73 K wide hysteresis below room temperature, which, upon solvent loss, decreased to a still remarkable 30 K wide hysteresis. Single crystal X-ray structures of two iron(II) coordination polymers and T-dependent powder XRD patterns are discussed to obtain insight into the structure property relationship of those materials.

Spin-crossover in an organic-inorganic hybrid perovskite.

The first spin-crossover (SCO) complex with an organic-inorganic hybrid perovskite structure (PPN)[Fe{Au(CN)2}3] (1) is reported, which displays three-step SCO behaviour. The light-induced excited spin-state trapping measurement gives T0 = 134 K for a three-dimensional FeL3-type (L = bis-monodentate ligand) SCO complex. Moreover, spin-state dependent fluorescence is observed in 1.

Solid state mononuclear divalent nickel spin crossover complexes.

Spin crossover complexes containing 3d4-3d7 transition metal ions with tunable electronic configurations in appropriate ligand field environments have been extensively investigated. In contrast, the development of 3d8 divalent nickel complexes displaying such a spin crossover behavior is far behind. The increasing number of X-ray single crystal structures along with magnetic evidence and thermodynamic equilibrium indicate that bistable divalent nickel complexes are gradually recognized to be a formal member of the "spin crossover family". Unfortunately, the rarity of nickel spin crossover complexes is occasionally mentioned. This Perspective article highlights examples of mononuclear 3d8 nickel spin crossover complexes in dynamic rearrangements with characterized solid state structures from the viewpoint of types of ligands utilized.

Tunable microwave absorption of switchable complexes operating near room temperature.

Materials that are able to switch microwave radiation are strongly desired for their potential applications in electronic devices. In this paper, we show the spin-dependant interaction of spin-crossover materials with microwave radiation, namely, the ability of coordination compounds [Fe(NH2trz)3]Br2 and [Fe(NH2trz)3](NO3)2 that undergo a cooperative spin transition between low-spin and high-spin states to operate as thermoswitchable microwave absorbers. The characteristics of the microwave reflection and transmission of these spin-crossover complexes were investigated at variable temperatures. The evolution of both the transmission and reflection spectra in the 26–37 GHz frequency band within the temperature range of spin crossover showed significant differences in the interaction of microwave radiation with the high-spin and low-spin forms of the compounds. The microwave transmission coefficient shows a notable decrease upon transition to the high-spin state, while the reflection coefficient can be both increased or decreased on the characteristic frequencies during the spin transition. The different microwave absorbing properties of the low-spin and high-spin forms are found to be associated with a notable microwave permittivity change upon spin crossover. The switchable microwave reflection/transmission correlates well with the transition characteristics found in the optical and differential scanning calorimetry measurements. These results widen the spectroscopic range in which spin-crossover materials can be applied and contribute to the creation of a preliminary database of the microwave absorbing properties of spin-crossover complexes.

Mechanical force-induced manipulation of electronic conductance in a spin-crossover complex: a simple approach to molecular electronics.

The atomic-scale technological sophistication from the last half-decade provides new avenues for the atom-by-atom fabrication of nanostructures with extraordinary precision. This urges the appraisal of the fabrication scheme layout for a modular nanoelectronic device based on an individual molecular complex. The mechanical force-induced distortion to the metal coordination sphere triggers a low-spin (LS) to high-spin (HS) electronic transition in the complex. The controlled structural distortions (relative to a specific bond-angle) are deemed to be the switching parameter for the observed spin-transitions. Mechanical stretching is the key to engineering a spin-state switch in the proposed molecular device. The spin-dependent reversible variation in the electronic conductance concurrent to the unique spin-states can be understood from the state-of-the-art Nonequilibrium Green's Function (NEGF) calculations. Combined with NEGF calculations, the DFT study further provides a qualitative perception of the electronic conductance in the two-terminal device architecture. From the transport calculations, there is also evidence of considerable fluctuation in the spin-dependent electronic conductance at the molecular junction with relative variations in the scattering limit. Subsequently, the present study shows significant advances in the transmission probabilities for the high-spin state of the Fe(ii) complex. The results empower the progress of nanoelectronics at the single molecule level.

A novel two-step Fe-Au type spin-crossover behavior in a Hofmann-type coordination complex {Fe(4-methylpyrimidine)2[Au(CN)2]2}.

A Hofmann-type two-step spin-crossover (SCO) complex with a pyrimidine derivative ligand, Fe(4-methylpyrimidine)2[Au(CN)2]2, was synthesized, and this complex shows a two-step SCO phenomenon in the intermediate state. Symmetry breaking also occurs in the intermediate state. These results reveal three spin states within the complex for high-spin (HS), HS0.5LS0.5, and low-spin (LS).

Thermal spin crossover in Fe(ii) and Fe(iii). Accurate spin state energetics at the solid state.

The thermal spin crossover (SCO) phenomenon refers to an entropy-driven spin transition in some materials based on d6-d9 transition metal complexes. While its molecular origin is well known, intricate SCO behaviours are increasingly common, in which the spin transition occurs concomitantly to e.g. phase transformations, solvent absorption/desorption, or order-disorder processes. The computational modelling of such cases is challenging, as it requires accurate spin state energies in the solid state. Density Functional Theory (DFT) is the best framework, but most DFT functionals are unable to balance the spin state energies. While a few hybrid functionals perform better, they are still too expensive for solid-state minima searches in moderate-size systems. The best alternative is to dress cheap local (LDA) or semi-local (GGA) DFT functionals with a Hubbard-type correction (DFT+U). However, the parametrization of U is not straightforward due to the lack of reference values, and because ab initio parametrization methods perform poorly. Moreover, SCO complexes undergo notable structural changes upon transition, so intra- and inter-molecular interactions might play an important role in stabilizing either spin state. As a consequence, the U parameter depends strongly on the dispersion correction scheme that is used. In this paper, we parametrize U for nine reported SCO compounds (five based on FeII, 1-5 and four based on FeIII, 6-9) when using the D3 and D3-BJ dispersion corrections. We analyze the impact of the dispersion correction treatments on the SCO energetics, structure, and the unit cell dimensions. The average U values are different for each type of metal ion (FeIIvs. FeIII), and dispersion correction scheme (D3 vs. D3-BJ) but they all show excellent transferability, with mean absolute errors (MAE) below chemical accuracy (i.e. MAE <4 kJ mol-1). This enables a better description of SCO processes and, more generally, of spin state energetics, in materials containing FeII and FeIII ions.

Reversible coordination-induced spin-state switching in complexes on metal surfaces.

Molecular spin switches are attractive candidates for controlling the spin polarization developing at the interface between molecules and magnetic metal surfaces1,2, which is relevant for molecular spintronics devices3-5. However, so far, intrinsic spin switches such as spin-crossover complexes have suffered from fragmentation or loss of functionality following adsorption on metal surfaces, with rare exceptions6-9. Robust metal-organic platforms, on the other hand, rely on external axial ligands to induce spin switching10-14. Here we integrate a spin switching functionality into robust complexes, relying on the mechanical movement of an axial ligand strapped to the porphyrin ring. Reversible interlocked switching of spin and coordination, induced by electron injection, is demonstrated on Ag(111) for this class of compounds. The stability of the two spin and coordination states of the molecules exceeds days at 4 K. The potential applications of this switching concept go beyond the spin functionality, and may turn out to be useful for controlling the catalytic activity of surfaces15.

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.

Simultaneous Spin-Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7',8,8'-Tetracyano-p-quinodimethane.

Invited for the cover of this issue are Ryuta Ishikawa and Satoshi Kawata at Fukuoka University and co-workers at Osaka University, Tohoku University, and Kumamoto University, Japan, collaborating within the research project "SOFT CRYSTALS". The image depicts the thermally induced simultaneous switching of magnetism and electrical conductivity in a two-dimensional supramolecular architecture composed of dinuclear FeII spin-crossover complexes and partially charged 7,7',8,8'-tetracyano-p-quinodimethanide radicals. 10.1002/chem.201903934.

Light-induced spin transition in the spin-crossover complex FePt2 detected by optical pump -coherent resonant nuclear elastic scattering

We report the results of optical pump-nuclear resonance probe experiments on the SCO complex [FeII(L-PtII(t-but-tpy))2](BF4)2 with L being 2,6-di(pyrazol-1-yl)-4-(trimethylsilylethynyl)pyridine) and t-but-tpy being 4,4′,4″-Tri-tert-Butyl-2,2′:6′,2″-terpyridine using a novel experimental set-up at the beamline P01, Petra III, DESY Hamburg. We investigate the changes in the spin state of the complex when it is excited by laser pulses of 766 nm wavelength and pulse width < 100 ps. Our simulations of the nuclear forward scattering data indicate a dominant low spin state along with some high spin fraction in the absence of laser pulses. We observe clear changes in the time-spectrum following the instant at which the laser pulse hits the sample. Furthermore, these alterations are recorded as the relative timing of the laser pulses with respect to the synchrotron pulses is varied.

Preparation and characterization of spin crossover thin solid films

Iron(II) spin crossover complexes display a reversible transition from low-spin (LS) state to high-spin (HS) state by e.g. variation of temperature, pressure or by irradiation with light. Therefore, these systems are promising candidates for information storage materials. In view of practical device applications thin films of these materials are needed. The SCO-compound [Fe(Htrz)2(trz)] (BF4) (1) switches between the LS and the HS state with a 50 K wide thermal hysteresis loop above room temperature. We have prepared thin films of 1 on a SiO2 substrate by spin coating. The spin states of the films have been characterized by Mossbauer spectroscopy in reflection mode using a MIMOS II spectrometer. A low quadrupole splitting (LS state) at 300 K and a high quadrupole splitting (HS state) at 400 K were found for the film, as well as for bulk powder of 1. This confirms that a spin crossover occurs above room temperature. Furthermore, synchrotron based nuclear resonance scattering measurements from 80 K to 400 K indicate that the hyperfine parameters are similar to those of the bulk powder of 1. DFT calculations reproduce the experimentally determined Fe-vibrational density of states of the bulk and of the thin film sample of 1. These results indicate that a higher fraction of HS Fe atoms is present in the film of 1. Therefore, we conclude different SCO properties of the thin film and the bulk material of 1.

Broad-Band Dielectric Spectroscopy Reveals Peak Values of Conductivity and Permittivity Switching upon Spin Crossover.

We use broad-band dielectric spectroscopy to investigate the spin-state dependence of electrical properties of the [Fe(Htrz)2(trz)](BF4) spin crossover complex. We show that the Havriliak-Negami theory can fully describe the variation of the complex dielectric permittivity of the material across the pressure-temperature phase diagram. The analysis reveals three dielectric relaxation processes, which we attribute to electrode/interface polarization, dipole relaxation, and charge transport relaxation. The contribution of the latter appears significant to the dielectric strength. Remarkably, the permittivity and conductivity changes between the high spin and low spin states are amplified at the corresponding relaxation frequencies.