Change In Spin State Research Articles

Phase equilibria in the YFeO3 – YСoO3 system in air

YFe1-xСоxO3 solid solutions were prepared by glycerol-nitrate technique. The homogeneity range of solid solutions was studied within the temperature range 1173 – 1573 K. A continues series of solid solution below the decomposition temperature of YСоO3, which was shown to be equal to 1266 ± 6 K, begins to narrow at higher temperatures and becomes equal to 0 ≤ x ≤ 0.1 at 1573 K. The phase diagram of the YFeO3 – YСoO3 system in the “T – composition” coordinates was divided into three fields. Similar to the parent ternary oxides, all single-phase YFe1-xСоxO3 solid solutions possess orthorhombically distorted perovskite structure (Pnma space group). Unusual behavior of orthorhombic distortions in YFe1-xСоxO3 with temperature was explained by probable changes in spin state of Co3+ ions.

Potential‐Induced Spin Changes in Fe/N/C Electrocatalysts Assessed by In Situ X‐ray Emission Spectroscopy

AbstractThe commercial success of the electrochemical energy conversion technologies required for the decarbonization of the energy sector requires the replacement of the noble metal‐based electrocatalysts currently used in (co‐)electrolyzers and fuel cells with inexpensive, platinum‐group metal‐free analogs. Among these, Fe/N/C‐type catalysts display promising performances for the reduction of O2 or CO2, but their insufficient activity and stability jeopardize their implementation in such devices. To circumvent these issues, a better understanding of the local geometric and electronic structure of their catalytic active sites under reaction conditions is needed. Herein we shed light on the electronic structure of the molecular sites in two Fe/N/C catalysts by probing their average spin state with X‐ray emission spectroscopy (XES). Chiefly, our in situ XES measurements reveal for the first time the existence of reversible, potential‐induced spin state changes in these materials.

Potential-Induced Spin Changes in Fe/N/C Electrocatalysts Assessed by In Situ X-ray Emission Spectroscopy.

The commercial success of the electrochemical energy conversion technologies required for the decarbonization of the energy sector requires the replacement of the noble metal-based electrocatalysts currently used in (co-)electrolyzers and fuel cells with inexpensive, platinum-group metal-free analogs. Among these, Fe/N/C-type catalysts display promising performances for the reduction of O2 or CO2 , but their insufficient activity and stability jeopardize their implementation in such devices. To circumvent these issues, a better understanding of the local geometric and electronic structure of their catalytic active sites under reaction conditions is needed. Herein we shed light on the electronic structure of the molecular sites in two Fe/N/C catalysts by probing their average spin state with X-ray emission spectroscopy (XES). Chiefly, our in situ XES measurements reveal for the first time the existence of reversible, potential-induced spin state changes in these materials.

Tunneling and Nonadiabatic Effects on a Proton-Coupled Electron Transfer Model for the Qo Site in Cytochrome bc1.

Cytochrome bc1 is a fundamental enzyme for cellular respiration and photosynthesis. This dimeric protein complex catalyzes a proton-coupled electron transfer (PCET) from the reduced coenzyme-Q substrate (Q) to a bimetallic iron-sulfur cluster in the Qo active site. Herein, we combine molecular dynamics simulations of the complete cytochrome bc1 protein with electronic-structure calculations of truncated models and a semiclassical tunneling theory to investigate the electron-proton adiabaticity of the initial reaction catalyzed in the Qo site. After sampling possible orientations between the Q substrate and a histidine side chain that functions as hydrogen acceptor, we find that a truncated model composed by ubiquinol-methyl and imidazole-iron(III)-sulfide captures the expected changes in oxidation and spin states of the electron donor and acceptor. Diabatic electronic surfaces obtained for this model with multiconfigurational wave function calculations demonstrate that this reaction is electronic nonadiabatic, and proton tunneling is faster than mixing of electronic configurations. These results indicate the formalism that should be used to calculate vibronic couplings and kinetic parameters for the initial reaction in the Qo site of cytochrome bc1. This framework for molecular simulation may also be applied to investigate other PCET reactions in the Q-cycle or in various metalloproteins that catalyze proton translocation coupled to redox processes.

Highly Z-Selective Double Bond Transposition in Simple Alkenes and Allylarenes through a Spin-Accelerated Allyl Mechanism.

Double-bond transposition in alkenes (isomerization) offers opportunities for the synthesis of bioactive molecules, but requires high selectivity to avoid mixtures of products. Generation of Z-alkenes, which are present in many natural products and pharmaceuticals, is particularly challenging because it is usually less thermodynamically favorable than generation of the E isomers. We report a β-dialdiminate-supported, high-spin cobalt(I) complex that can convert terminal alkenes, including previously recalcitrant allylbenzenes, to Z-2-alkenes with unprecedentedly high regioselectivity and stereoselectivity. Deuterium labeling studies indicate that the catalyst operates through a π-allyl mechanism, which is different from the alkyl mechanism that is followed by other Z-selective catalysts. Computations indicate that the triplet cobalt(I) alkene complex undergoes a spin state change from the resting-state triplet to a singlet in the lowest-energy C-H activation transition state, which leads to the Z product. This suggests that this change in spin state enables the catalyst to differentiate the stereodefining barriers in this system, and more generally that spin-state changes may offer a route toward novel stereocontrol methods for first-row transition metals.

Spin Change of Asteroid 2012 TC4 Probably by Radiation Torques

Abstract Asteroid 2012 TC4 is a small (∼10 m) near-Earth object that was observed during its Earth close approaches in 2012 and 2017. Earlier analyses of light curves revealed its excited rotation state. We collected all available photometric data from the two apparitions to reconstruct its rotation state and convex shape model. We show that light curves from 2012 and 2017 cannot be fitted with a single set of model parameters; the rotation and precession periods are significantly different for these two data sets, and they must have changed between or during the two apparitions. Nevertheless, we could fit all light curves with a dynamically self-consistent model assuming that the spin states of 2012 TC4 in 2012 and 2017 were different. To interpret our results, we developed a numerical model of its spin evolution in which we included two potentially relevant perturbations: (i) gravitational torque due to the Sun and Earth and (ii) radiation torque, known as the Yarkovsky–O’Keefe–Radzievskii–Paddack (YORP) effect. Despite our model simplicity, we found that the role of gravitational torques is negligible. Instead, we argue that the observed change of its spin state may be plausibly explained as a result of the YORP torque. To strengthen this interpretation, we verify that (i) the internal energy dissipation due to material inelasticity and (ii) an impact with a sufficiently large interplanetary particle are both highly unlikely causes of its observed spin state change. If true, this is the first case where the YORP effect has been detected for a tumbling body.

Halogenation affects driving forces, reorganization energies and "rocking" motions in strained [Fe(tpy)2]2+ complexes.

Controlling the energetics of spin crossover (SCO) in Fe(II)-polypyridine complexes is critical for designing new multifunctional materials or tuning the excited-state lifetimes of iron-based photosensitizers. It is well established that the Fe-N "breathing" mode is important for intersystem crossing from the singlet to the quintet state, but this does not preclude other, less obvious, structural distortions from affecting SCO. Previous work has shown that halogenation at the 6 and 6'' positions of tpy (tpy = 2,2';6',2''-terpyridine) in [Fe(tpy)2]2+ dramatically increased the lifetime of the excited MLCT state and also had a large impact on the ground state spin-state energetics. To gain insight into the origins of these effects, we used density functional theory calculations to explore how halogenation impacts spin-state energetics and molecular structure in this system. Based on previous work we focused on the ligand "rocking" motion associated with SCO in [Fe(tpy)2]2+ by constructing one-dimensional potential energy surfaces (PESs) along the tpy rocking angle for various spin states. It was found that halogenation has a clear and predictable impact on ligand rocking and spin-state energetics. The rocking is correlated to numerous other geometrical distortions, all of which likely affect the reorganization energies for spin-state changes. We have quantified trends in reorganization energy and also driving force for various spin-state changes and used them to interpret the experimentally measured excited-state lifetimes.

Reactivity of a T-shaped cobalt(I) pincer-complex.

The reactivity of a paramagnetic T-shaped cobalt(i) complex, [(iPrboxmi)Co], stabilised by a monoanionic bis(oxazolinylmethylidene)-isoindolate (boxmi) NNN pincer ligand is described. The exposure to carbon monoxide as an additional neutral ligand resulted in the square-planar species [(iPrboxmi)Co(CO)], accompanied by a change in the electronic spin state from S = 1 to S = 0. In contrast, upon treatment with trimethylphosphine the formation of the distorted tetrahedral complex [(iPrboxmi)Co(PMe3)] was observed (S = 1). Reacting [(iPrboxmi)Co] with iodine (I2), organic peroxides (tBu2O2, (SiMe3)2O2) and diphenyldisulphide (Ph2S2) yielded the tetracoordinated complexes [(iPrboxmi)CoI], [(iPrboxmi)Co(OtBu)], [(iPrboxmi)Co(OSiMe3)] and [(iPrboxmi)Co(SPh)], respectively, demonstrating the capability of the boxmi-supported cobalt(i) complex to homolytically cleave bonds and thus its distinct one-electron reactivity. Furthermore, a square-planar cobalt(ii) alkynyl complex [(iPrboxmi)Co(CCArF)] was identified as the main product in the reaction between [(iPrboxmi)Co] and a terminal alkyne, 4-fluoro-1-ethynylbenzene. Putting such species in the context of the previously investigated hydroboration catalysis, its stoichiometric reaction with pinacolborane revealed its potential conversion into a cobalt(ii) hydride complex, thus confirming its original attribution as off-cycle species.

A diamagnetic iron complex and its twisted sister - structural evidence on partial spin state change in a crystalline iron complex.

We report here the syntheses of a diamagnetic Fe complex [Fe(HL)2] (1), prepared by reacting a redox non-innocent ligand precursor N,N'-bis(3,5-di-tert-butyl-2-hydroxy-phenyl)-1,2-phenylenediamine (H4L) with FeCl3, and its phenoxazine derivative [Fe(L')2] (2), which was obtained via intra-ligand cyclisation of the parent complex. Magnetic measurements, accompanied by spectroscopic, structural and computational analyses show that 1 can be viewed as a rather unusual Fe(III) complex with a diamagnetic ground state in the studied temperature range due to a strong antiferromagnetic coupling between the low-spin Fe(III) ion and a radical ligand. For a paramagnetic high-spin Fe(II) complex 2 it was found that, when crystalline, it undergoes a thermally induced process where 25% of the molecules in the material change to a diamagnetic low-spin ground state below 100 K. Single crystal X-ray studies conducted at 95 K afforded detailed structural evidence for this partial change of spin state of 2 showing the existence of crystallographically distinct molecules in a 3 : 1 ratio which exist in high- and low-spin states, respectively. Also, the magnetic behaviour of 2 was found to be related with the crystallinity of the material as demonstrated by near-IR radiation to unpaired electrons conversion ability of amorphous sample of 2.

Spin unlocking oxygen evolution reaction on antiperovskite nitrides

The spin state change of Fe3+ ions induced the paramagnetic Fe0.5Ni0.5OOH shell on the ferromagnetic Cu0.5NFe3Ni0.5 core via superexchange interaction, facilitating charge transfer and oxygen species ad(de)sorption for boosted OER performance.

DFT computational insight into the mechanism of the monomer–trimer isomerism of Ni(II) bis-acetylacetonate

The possible reaction paths for the spin-forbidden dissociation of paramagnetic nickel(II) bis-acetylacetonate trimer (Ni(acac)2) have been studied based on the DFT UB3LYP/6-311++G(d,p) calculations. Two energy preferred reaction routes involve three consecutive steps resulting in spin state changes of the system: (S = 3) → (S = 2) → (S = 1) → (S = 0). The highest theoretically-estimated limits for energy barriers necessary to overcome along these routes, as estimated by the relative energies of the minimum energy crossing points (MECPs) on the seams of the intersecting potential energy surfaces of different multiplicity, do not exceed the value of 33 kcal/mol. The results obtained are in a good agreement with available experimental data. The considered dissociation – association rearrangement represents an example of a thermally induced multi-step Coordination-Induced Spin-State Switching phenomenon.

Acidity-Driven Bidirectional Room-Temperature Spin-State Switch and Fluorescence Modulation of a Mononuclear Fe(II) Complex

Room-temperature switchable materials showing multiple responses toward external stimuli are highly desired. Herein, we report bidirectional spin-state switch and fluorescence modulation of an Fe(I...

Modulation of Nuclearity in CuII -MnII Complexes of a N2 O2 Donor Ligand Depending upon Carboxylate Anions: Structures, Magnetic Properties and Catalytic Oxidase Activities.

Three new hetero-metallic copper(II)-manganese(II) complexes, [(CuL)2 Mn3 (C6 H5 CO2 )6 ] (1), [(CuL)2 Mn(CH3 CO2 )2 ] (2), and {[(CuL)2 Mn(C6 H5 CH2 CO2 )2 ] ⋅ 2CH3 CN} (3), have been synthesized using [CuL] as ''metalloligand'' (where H2 L=N,N'-bis(2-hydroxynaphthyl-methylidene)-1,3-propanediamine). Single-crystal structural analyses show an almost linear penta-nuclear structure for complex 1 where a square planar [CuL] unit is connected to each of the two terminal MnII ions of a linear, centrosymmetric [Mn3 (benzoate)6 ] unit through the double phenoxido bridges. Both complexes 2 and 3 possess a linear tri-nuclear structure where two terminal square-pyramidal [CuL] units are bonded to the central MnII ion through double phenoxido oxygen atoms along with a syn-syn bridging acetate (for 2)/phenyl acetate (for 3). All three complexes exhibit catecholase, and phenoxazinone synthase-like activities under aerial conditions. For catecholase like activity, the turnover numbers (kcat ) are 595, 40, and 205 h-1 whereas, for phenoxazinone synthase like activity, the turnover numbers are 25, 4, and 11 h-1 for complexes 1-3, respectively. The mechanism of both catalytic oxidase activities is proposed on the basis of mass spectral evidences. Variable-temperature (2-300 K) dc molar magnetic susceptibility measurements of 1 reveal antiferromagnetic interactions between the Cu-Mn centres (J1 =-29.3 cm-1 ), and also between the Mn-Mn centres of the [Mn3 (benzoate)6 ] unit (J2 =-0.68 cm-1 ). On increasing the magnetic field at 2 K, its ground spin state changes from S=3/2 to S=5/2 at 4 T, attributable to the low value of J2 which makes the excited spin states close in energy with the ground spin state. Complexes 2 and 3 show antiferromagnetic coupling interactions between the Cu-Mn pairs with J values of -9.51, and -5.32 cm-1 , respectively.

Ligand-Mediated Spin-State Changes in a Cobalt-Dipyrrin-Bisphenol Complex.

The influence of a redox-active ligand on spin-changing events induced by the coordination of exogenous donors is investigated within the cobalt complex [CoII(DPP·2–)], bearing a redox-active DPP2– ligand (DPP = dipyrrin-bis(o,p-di-tert-butylphenolato) with a pentafluorophenyl moiety on the meso-position. This square-planar complex was subjected to the coordination of tetrahydrofuran (THF), pyridine, tBuNH2, and AdNH2 (Ad = 1-adamantyl), and the resulting complexes were analyzed with a variety of experimental (X-ray diffraction, NMR, UV–visible, high-resolution mass spectrometry, superconducting quantum interference device, Evans’ method) and computational (density functional theory, NEVPT2-CASSCF) techniques to elucidate the respective structures, spin states, and orbital compositions of the corresponding octahedral bis-donor adducts, relative to [CoII(DPP·2–)]. This starting species is best described as an open-shell singlet complex containing a DPP·2– ligand radical that is antiferromagnetically coupled to a low-spin (S = 1/2) cobalt(II) center. The redox-active DPPn– ligand plays a crucial role in stabilizing this complex and in its facile conversion to the triplet THF adduct [CoII(DPP·2–)(THF)2] and closed-shell singlet pyridine and amine adducts [CoIII(DPP3–)(L)2] (L = py, tBuNH2, or AdNH2). Coordination of the weak donor THF to [CoII(DPP·2–)] changes the orbital overlap between the DPP·2– ligand radical π-orbitals and the cobalt(II) metalloradical d-orbitals, which results in a spin-flip to the triplet ground state without changing the oxidation states of the metal or DPP·2– ligand. In contrast, coordination of the stronger donors pyridine, tBuNH2, or AdNH2 induces metal-to-ligand single-electron transfer, resulting in the formation of low-spin (S = 0) cobalt(III) complexes [CoIII(DPP3–)(L)2] containing a fully reduced DPP3– ligand, thus explaining their closed-shell singlet electronic ground states.

Magnetic transformation of Mn from anti-ferromagnetism to ferromagnetism in FeCoNiZMnx (Z = Si, Al, Sn, Ge) high entropy alloys

We design high entropy alloys (HEAs) with different induction elements (Si/Al/Sn). In order to keep the crystal structure invariant and to investigate how the increment in saturation magnetization (Ms) is caused only by the change of electron spin state, each set of HEAs contains a different amount of Mn. Synergistic effects among induction elements that induce the magnetic transformation of Mn from anti-ferromagnetism to ferromagnetism are found. Ms of added Mn reduces when a particular induction element (Si0.4/Al0.4/Sn0.4) exists, while a larger increment of Ms appears when two induction elements coexist, Si0.4Al0.4 (25.79 emu/g) and Sn0.4Al0.4 (15.43 emu/g). This is reflected in the microcosmic magnetic structure for the emergence of closed domains due to large demagnetization energy, which is confirmed by the Lorentz transmission electron microscope (LTEM) data. The calculated magnetic moments and the exchange integral constants from density functional theory based on the Exact Muffin-Tin Orbits formalism reveal that the magnetic state and the strength of ferromagnetic and anti-ferromagnetic coupling determine the variation of Ms in different chemical environments. The difference in energy levels of coexisting multiple induction elements also leads to a larger increment of Ms, Si0.4Al0.4Sn0.4 (29.78 emu/g), and Si0.4Al0.4Ge0.4Sn0.4 (31.00 emu/g).

Magnetoelastic properties and behaviour of 4C pyrrhotite, Fe7S8, through the Besnus transition

Pyrrhotite, Fe7S8, is a commonly occurring carrier of magnetic remanence and has a low temperature transition, the Besnus transition, involving a change in spin state. Variations of the thermodynamic, magnetic and elastic properties through this transition at ∼33 K in a natural sample of 4C pyrrhotite have been tested against a group theoretical model for coupling between order parameters relating to Fe/vacancy ordering (irrep U1(1/2,0,1/4)) and magnetic ordering (irreps m and m). Magnetoelastic coupling is weak but the pre-existing microstructure of ferroelastic and magnetic domains, that develop as a consequence of Fe/vacancy and ferrimagnetic ordering during slow cooling in nature (P63/mmc → C2′/c′), causes subtle changes in the low temperature transition (C2′/c′ → P). The Besnus transition involves a rotation of magnetic moments out of the a–c plane of the monoclinic structure, but it appears that the transition temperature might vary locally according to whether it is taking place within the pre-existing domain walls or in the domains that they separate. Evidence of metamagnetic transitions suggests that the magnetic field–temperature phase diagram will display some interesting diversity. Low temperature magnetic transitions in minerals of importance to the palaeomagnetism community have been used to identify the presence of magnetite and haematite in rocks and the Besnus transition is diagnostic of the existence of pyrrhotite, Fe7S8.

Spin–orbit torque field-effect transistor (SOTFET): Proposal for a magnetoelectric memory

Spin-based memories are attractive for their non-volatility and high durability but provide modest resistance changes, whereas semiconductor logic transistors are capable of providing large resistance changes, but lack memory function with high durability. The recent availability of multiferroic materials provides an opportunity to directly couple the change in spin states of a magnetic memory to a charge change in a semiconductor transistor. In this work, we propose and analyze the spin–orbit torque field-effect transistor, a device with the potential to significantly boost the energy efficiency of spin-based memories and to simultaneously offer a palette of functionalities.

Effect of Ligand Field Strength on the Spin Crossover Behaviour in 5-X-SalEen (X=Me, Br and OMe) Based Fe(III) Complexes.

The reaction of Fe(NCS)3 prepared in situ in MeOH with 5-X-SalEen ligands (5-X-SalEen=condensation product of 5-substituted salicylaldehyde and N-ethylethylenediamine) provided three Fe(III) complexes, [Fe(5-X-SalEen)2 ]NCS; X=Me (1), X=Br (2), X=OMe (3). All the complexes reveal similar structural features but a very different magnetic profile. Complex 1 shows a gradual spin crossover while complexes 2 and 3 show a sharp spin transition. The T1/2 for complex 2 is 237 K while for complex 3 it is much higher with a value of 361 K. The spin transition temperature is shifted towards higher temperature with increasing electron-donation ability of the ligand substituents. This experimental observation has been rationalized with DFT calculations. UV-Vis and cyclic voltammetry studies support the fact that the electron density on the ligand increases from Me to Br to OMe substituents. To understand the change in spin states, temperature-dependent EPR spectra have been recorded. The spin state equilibrium in the liquid state has been probed with Evans NMR spectroscopic method, and thermodynamic parameters have been evaluated for all complexes.

Anomalous High Temperature Structural Behavior of Potential Multifunctional Material SmCo0.5Cr0.5O3

Crystal structure parameters of the mixed cobaltite–chromite SmCo0.5Cr0.5O3 in the temperature range of 298–1173 K were derived from in situ high‐resolution X‐ray synchrotron powder diffraction data. Similar to the parent SmCoO3 compound, SmCo0.5Cr0.5O3 reveals anomalous thermal expansion reflected in abnormal temperature dependence of the unit cell dimensions and the selected interatomic distances and angles. These anomalies are associated with temperature induced changes of spin state of Co3+ ions and coupled insulator‐metal transition. Observed decreasing behavior of the bandwidth W points on the increasing population of the exited spin states of Co3+ ions in SmCo0.5Cr0.5O3 with increasing temperature. First principle calculations revealed antiferromagnetic ground state of SmCo0.5Cr0.5O3 as the most stable.

Spin–state transition in the layered barium cobaltite derivatives and their thermoelectric properties

Ba1.9Me0.1Co9O14 (Me = Ba, Sr, Ca) (BCO) layered cobaltites were prepared by means of solid-state reactions method. Crystal structure, microstructure, thermal expansion, electrical conductivity, and thermo-EMF for the obtained oxides were studied; the values of their linear thermal expansion coefficient, activation energy of electrical transport, and power factor values were calculated. It was found that BCO are p-type semiconductors, in which the spin-state transition occurs within 460-700 K temperature interval due to change in spin state of cobalt ions, which accompanied the sharp increase in electrical conductivity, activation energy of electrical conductivity, and linear thermal expansion coefficient, while thermo-EMF coefficient decreased. Partial substitution of barium by strontium or calcium in BCO leads to the increase in spin-state transition temperature and electrical conductivity of the samples, and, at the same time, thermo-EMF coefficient; consequently, their power factor values decrease.