High-spin States Research Articles

High-Spin State of a Ferrocene Electron Donor Revealed by Optical and X-ray Transient Absorption Spectroscopy.

Ferrocene is one of the most common electron donors, and mapping its ligand-field excited states is critical to designing donor-acceptor (D-A) molecules with long-lived charge transfer states. Although 3(d-d) states are commonly invoked in the photophysics of ferrocene complexes, mention of the high-spin 5(d-d) state is scarce. Here, we provide clear evidence of 5(d-d) formation in a bimetallic D-A molecule, ferrocenyl cobaltocenium hexafluorophosphate ([FcCc]PF6). Femtosecond optical transient absorption (OTA) spectroscopy reveals two distinct electronic excited states with 30 and 500 ps lifetimes. Using a combination of ultraviolet, visible, near-infrared, and short-wave infrared probe pulses, we capture the spectral features of these states over an ultrabroadband range spanning 320 to 2200 nm. Time-dependent density functional theory (DFT) calculations of the lowest triplet and quintet states, both primarily Fe(II) (d-d) in character, qualitatively agree with the experimental OTA spectra, allowing us to assign the 30 ps state as the 3(d-d) state and the 500 ps state as the high-spin 5(d-d) state. To confirm the ferrocene-centered high-spin character of the 500 ps state, we performed X-ray transient absorption (XTA) spectroscopy at the Fe and Co K edges. The Fe K-edge XTA spectrum at 150 ps shows a red shift of the absorption edge that is consistent with an Fe(II) high-spin state, as supported by ab initio calculations. The transient signal detected at the Co K-edge is 50× weaker, confirming the ferrocene-centered character of the excited state. Fitting of the transient extended X-ray absorption fine structure region yields an Fe-C bond length increase of 0.25 ± 0.1 Å in the excited state, as expected for the high-spin state based on DFT. Altogether, these results demonstrate that the high-spin state of ferrocene should be considered when designing donor-acceptor assemblies for photocatalysis and photovoltaics.

Impact of ligand substituents on the spiral arrangement in glutarohydrazide-based binuclear-iron(II) helicates

Coordination-driven self-assembly, particularly, helical metal complexes are quite interesting considering their distinctive architectures. Herein, we assemble new Fe(II) compounds namely, [Fe2(L1)2](BF4)4·2H2O, 1 and [Fe2(L2)2](BF4)4, 2 from flexible glutarohydazide ligands featuring helical-like di-nuclear arrays. Structurally, in all the compounds, the two chelating ligands were arranged differently, i.e. inverted U-shaped conformation for 1 and a twisted spiral arrangement for 2 were observed respectively. Interestingly, the observed structural variations of all compounds are a result of the ligand substituents in the six positions of the pyridyl moiety in which the relatively bulky methyl group substituted ligand resists the spiral arrangement which was observed in the Br substituted analog. Magnetic investigations revealed that compounds 1 and 2 are in the high spin state at all the measured temperature ranges. Further ligand fine-tunings in the pyridyl-aldehyde moiety for the presented helical-like arrays bearing relatively strong ligand field strength are suggested for achieving the spin crossover (SCO) event.

Photo-Excited High-Spin State Ni (III) Species in Mo-Doped Ni3S2 for Efficient Urea Oxidation Reaction.

Designing robust catalystsfor increasing the sluggish kinetics of the urea oxidation reaction (UOR) is challenging. Herein, the regulation of spin states for metal active sites by photoexcitation to facilitate the adsorption of urea and intermediates is demonstrated. Mo-doped nickel sulfide nanoribbon arrays (Mo-Ni3S2@NMF) with excellent light-trapping capacity are successfully prepared. Under AM 1.5G illumination, the activity of the Mo-Ni3S2@NMF exhibits a 50% improvement in the UOR current. Compared with those under dark conditions, Mo-Ni3S2@NMF achieve 10mA cm-2 at 1.315 VRHE for UOR and 1.32 Vcell for urea electrolysis, which are decreases of 15 and 80mV, respectively. The electron spin resonance, in situ Fourier transform infrared spectroscopy analysis and density functional theorycalculations reveal that illumination led to the formation of Ni3+ active sites in a high-spin state, which strengthens the d-p orbital hybridization of Ni-N, hence facilitating the adsorption of urea. C─N cleavage of the *CONN intermediate is further inhibited, which promotes the oxidation of urea molecules via the active N2 pathway, thereby accelerating the UOR rate.

Spectroscopic evidence of spin-state excitation in d-electron correlated semiconductor FeSb2

Iron antimonide (FeSb2) has been investigated for decades due to its puzzling electronic properties. It undergoes the temperature-controlled transition from an insulator to an ill-defined metal, with a cross-over from diamagnetism to paramagnetism. Extensive efforts have been made to uncover the underlying mechanism, but a consensus has yet to be reached. While macroscopic transport and magnetic measurements can be explained by different theoretical proposals, the essential spectroscopic evidence required to distinguish the physical origin is missing. In this paper, through the use of X-ray absorption spectroscopy and atomic multiplet simulations, we have observed the mixed spin states of 3d 6 configuration in FeSb2. Furthermore, we reveal that the enhancement of the conductivity, whether induced by temperature or doping, is characterized by populating the high-spin state from the low-spin state. Our work constitutes vital spectroscopic evidence that the electrical/magnetical transition in FeSb2 is directly associated with the spin-state excitation.

A deeper orbital hybridization because of more unpaired electrons in d orbital resulted in a better catalytic performance

Previous reports usually co-doping various additional transition metals to improve the NH3-SCR performance of V/TiO2 catalyst. However, seldom work understood the so-called enhancement from an atom scale. This work first selected nine elements (Me) mainly from a same VIB family or a same fourth period, and compared them in transition states of MeV/TiO2 during NH3-SCR. The dehydrogenation step of adsorbed NH3 resulted to be the key step and W substitution got the lowest dehydrogenation energy of 1.29 eV. After estimating the key atoms, the total width of Me-O-V hybridization followed the order of 1.7 eV (WV/TiO2) > 1.3 eV (V/TiO2) > 1.1 eV (CoV/TiO2) > 0.9 eV (LaV/TiO2). The deeper hybridization was attributed to a shorter Me-O-V bond. Both V and W were in a high-spin state while Co and La were in a low-spin state. Moreover, W atom had four semi full d orbitals, bigger than that (three) of V, which were more conducive to electron transfer, and resulting in the biggest overlapping of atomic orbitals. The above prediction was consistent with the afterward experimental result, in which MeV/TiO2 showed a NH3-SCR conversion order of 81 % (WV/TiO2) > 59 % (V/TiO2) > 41 % (CoV/TiO2) > 2 % (LaV/TiO2) at 300 °C. The main result of this work is in favor of designing an effective catalyst from the atom scale.

Cobalt(II)-Substituted Cysteamine Dioxygenase Oxygenation Proceeds through a Cobalt(III)-Superoxo Complex.

We investigated the metal-substituted catalytic activity of human cysteamine dioxygenase (ADO), an enzyme pivotal in regulating thiol metabolism and contributing to oxygen homeostasis. Our findings demonstrate the catalytic competence of cobalt(II)- and nickel(II)-substituted ADO in cysteamine oxygenation. Notably, Co(II)-ADO exhibited superiority over Ni(II)-ADO despite remaining significantly less active than the natural enzyme. Structural analyses through X-ray crystallography and cobalt K-edge excitation confirmed successful metal substitution with minimal structural perturbations. This provided a robust structural basis, supporting a conserved catalytic mechanism tailored to distinct metal centers. This finding challenges the proposed high-valent ferryl-based mechanism for thiol dioxygenases, suggesting a non-high-valent catalytic pathway in the native enzyme. Further investigation of the cysteamine-bound or a peptide mimic of N-terminus RGS5 bound Co(II)-ADO binary complex revealed the metal center's high-spin (S = 3/2) state. Upon reaction with O2, a kinetically and spectroscopically detectable intermediate emerged with a ground spin state of S = 1/2. This intermediate exhibits a characteristic 59Co hyperfine splitting (A = 67 MHz) structure in the EPR spectrum alongside UV-vis features, consistent with known low-spin Co(III)-superoxo complexes. This observation, unique for protein-bound thiolate-ligated cobalt centers in a protein, unveils the capacities for O2 activation in such metal environments. These findings provide valuable insights into the non-heme iron-dependent thiol dioxygenase mechanistic landscape, furthering our understanding of thiol metabolism regulation. The exploration of metal-substituted ADO sheds light on the intricate interplay between metal and catalytic activity in this essential enzyme.

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (CpiPr5)2Ho2I3.

Mixed-valence dilanthanide complexes of the type (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln-Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (CpiPr5)2Ln2I3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln-Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin-spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide-lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm-1. Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo5 and Nd2Fe14B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers.

β decay of the ground state and of a low-lying isomer in Bi216

A detailed β-decay study of the low- and high-spin states in Bi216 has been performed at the ISOLDE Decay Station at the CERN-ISOLDE facility. In total, 48 new levels and 83 new transitions in the β-decay daughter Po216 were identified. Shell-model calculations for excited states in Bi216 and Po216 were performed using the H208 and the modified Kuo-Herling particle effective interactions. Based on the experimental observations and the shell-model calculations, the most likely spin and parity assignments for the β-decaying states in Bi216 are (3−) and (8−), respectively. Published by the American Physical Society 2024

Why high spin? Why sulphur? Comparative analysis of catalytic oxidation by Compound I of cytochrome P450, catalase, peroxidase, and selenocysteine-modified P450

Compound I, which is formed in the catalytic cycle of cytochrome P450 enzymes, is best described as a high-spin state (S = 3/2) rather than a low-spin state (S = 1/2). Its high-spin role in catalytic oxidation (R−H → R−OH) remains poorly understood (why high spin?). Catalase and peroxidase can both generate Compound I. The axial ligand of cysteine thiolate R−S− (P450) at the haem site may be responsible for P450′s unique catalytic oxidation, as opposed to tyrosinate R−O− (catalase) or histidine imidazolate R−N− (peroxidase) or selenocysteine selenolate R−Se− (why sulphur?). This study aimed to address these two questions by density functional theory calculations (PBE-D3BJ-gCP/def2-SVP) of the reactions between Compound I and CH4. The results indicate that the stability of the adducts X−Fe−OH–-–CH3 (where X = Se, S, O, and N), which are produced from abstracting H from CH4 by X−Fe=O, can provide insights into these two issues.

Preparation of LiLaZrMO (M= Ga/Al) solid electrolytes for thermal batteries

Thermal batteries (TBs) are ideal power sources for high temperature environment due to their high specific energy, long storage time, and quick activation. However, the common molten salt electrolytes (MSE) suffer from overflow under overload or high spin state, which could lead to short circuit of the batteries. To address this issue, LiLaZrMO (LLZMO, M = Ga/Al) doped with different elements are prepared. The doping elements result in the phase change of LiLaZrO (LLZO) from tetragonal to cubic, alters the distribution of Li atoms and increases the ion transport bottleneck sizes. In particular, LiLaZrGaO (LLZGO) has the lowest activation energy (0.3 eV) and the highest total conductivity (2.57 × 10−2 S cm−1 at 500 °C) owing to the larger bottleneck and unique Li+ transport channel. TB with LLZGO provides the highest discharge specific capacity of 368.5 mAh g−1 and lowest internal resistance (0.23 Ω cm−2). Compared with the ones using LiF–LiCl–LiBr MSE, TB with LLZGO solid electrolyte (SE) also shows superior performance in pulse discharge capabilities due to the stable internal resistance as well as the fluctuation free characteristics. Therefore, LLZGO SE holds great potential as viable alternative to MSEs in TBs.

Analyzing trade-off issues in synthesis of magnetic polymer compounds through theoretical investigation

Incorporating magnetic species, magnetic functional groups or additives, into polymer hosts is an effective method for synthesizing magnetic polymers. Polymers can gain magnetic moments not solely through magnetic coupling but also via the induction of Coulombic excitation. Attachment of the magnetic side-groups to the polymer backbone increases orbital localization in repeat units. This will bring two competing effects. The orbital localization will increase the intra-site Coulomb interaction, which increases magnetic moments in repeat units. Oppositely, the orbital localization also increases the energy splitting between orbitals on the polymer backbone and on side-groups, suppressing thus the magnetic moments of repeat units. However, a preference for low-spin states in the polymer units emerges when a substantial split in orbital energy occurs due to a strong coupling, consequently suppressing the magnetic moment. On the contrary, a minimal split in orbital energy within the polymer units can readily induce a high-spin state and generate a magnetic moment. However, in such cases, the Coulomb interaction triggered by the interconnected magnetic moieties might be too weak to produce a magnetic moment in the polymer. To explore this trade-off, we have proposed a theoretical two-level model aimed at elucidating the decision-making process of experimentalists during the synthesis of magnetic polymers. We also found that the dimerization of the polymer backbone together with the phonon dependence of spin–spin interaction between near-neighbor repeat units increases magnetic moments. As the magnetic responses arising from Coulombic interactions in polymers are intricately linked to carrier density, properties of the magnetic polymers acting as an active layer of a field-effect transistor can be tuned by the gate field, which controls the charge carrier density in the transistor transport channel.

High-field/high-frequency electron spin resonances of Fe-doped β−Ga2O3 by terahertz generalized ellipsometry: Monoclinic symmetry effects

We demonstrate detection and measurement of electron paramagnetic spin resonances (EPR) of iron defects in β−Ga2O3 utilizing generalized ellipsometry at frequencies between 110 and 170 GHz. The experiments are performed on an Fe-doped single crystal in a free-beam configuration in reflection at 45∘ and magnetic fields between 3 and 7 T. In contrast with low-field, low-frequency EPR measurements, we observe all five transitions of the s=5/2 high-spin state Fe3+ simultaneously. We confirm that ferric Fe3+ is predominantly found at octahedrally coordinated Ga sites. We obtain the full set of fourth-order monoclinic zero-field splitting parameters for both octahedrally and tetrahedrally coordinated sites by employing measurements at multiple sample azimuth rotations. The capability of high-field EPR allows us to demonstrate that simplified second-order orthorhombic spin Hamiltonians are insufficient, and fourth-order terms as well as consideration of the monoclinic symmetry are needed. These findings are supported by computational approaches based on density-functional theory for second-order and on ligand-field theory for fourth-order parameters of the spin Hamiltonian. Terahertz ellipsometry is a way to measure spin resonances in a cavity-free setup. Its possibility of varying the probe frequency arbitrarily without otherwise changing the experimental setup offers unique means of truly disentangling different components of highly anisotropic spin Hamiltonians. Published by the American Physical Society 2024

Constructing Alkyl Chain Modified FeII Spin Crossover Complexes through Complementary Pair Strategy

AbstractFour alkyl chains and cyclohexane modified FeII complexes [Fe(Ln)(L’)](ClO4)2⋅solv (n=1, 2, 3, 4) were synthesized and characterized. X‐ray diffraction study showed that these complexes were constituted by asymmetric mononuclear FeII entities, incorporating alkyl‐chain‐modified bppCOOH (2,6‐bis(1H‐pyrazol‐1‐yl)isonicotinic acid) ligands and 6,6’’‐2,6‐dimethoxyphenyl‐substituted terpy ligand (L’). Magnetic susceptibility measurements revealed that complexes 1, 2, and 3 were in the high spin state across the measured temperature range, whereas complex 4 displayed an incomplete spin crossover phenomenon, with a transition temperature (T1/2) at 240 K. Investigations into variable‐temperature structure and magneto‐structural correlations revealed that the integration of alkyl‐chain‐modified bipyridyl units fostered the π⋅⋅⋅π intra‐ and intermolecular interactions, contributing to distinct crystal stacking and spatial configurations in complex 4 when compared to its counterparts. These findings underscore the pivotal influence of intramolecular interactions on the FeII spin states and highlight the significance of designing flexible ligands for modulating spin‐crossover characteristics.

Investigation of optical and magnetic properties of 3d-4d transition metal ion based double Perovskite: Sr2MnRuO6

Investigation of physical properties in double perovskites, A2B′B″O6, containing 3d/4d transition metal ions at the B sites is an interesting avenue of research. In this study, we focus on Sr2MnRuO6, exploring its structural, morphological, optical and magnetic properties. Sr2MnRuO6 was synthesized in single phase using solid-state reaction route. It crystallizes in a tetragonal structure (space group I4/mcm, #140) with lattice parameters a = 5.4633 (2) Å, c = 7.9419 (1) Å. X-ray diffraction analysis revealed no super lattice reflections, indicating disorder in the B-site cations.The Jahn-Teller distortion in Mn-O6 octahedra,as revealed by XRD results, indicates a high spin state for the Mn3+ ion. The stoichiometric ratio of Sr: Mn: Ru (∼2:1:1), as determined by bond valence sum calculations and confirmed by energy dispersive x-ray spectroscopy agree well with the nominal composition of Sr2MnRuO6. Diffuse reflectance spectroscopy showed strong absorption throughout the visible region with a direct band gap of ∼3 eV, indicating Sr2MnRuO6 is a potential candidate for optical applications. Huge photoluminescence emission observed in the visible region is attributed to Mn3+ ions. The temperature dependence of molar susceptibility data indicates a paramagnetic to antiferromagnetic transition around 195 K. The possible super exchange paths for antiferromagnetic interaction are Ru5+- 4d3 (t2g3eg0) − O1 − Ru5+- 4d3 (t2g3eg0) along the z axis, or Ru5+- 4d3 (t2g3eg0) − O2 − Ru5+- 4d3 (t2g3eg0) in the xy-plane, with the angles between these orbitals being nearly 180°. At low temperatures under a 10,000 Oe field, spin glass type magnetic behaviour is observed. The effective magnetic moment (6.17 μB) obtained from the Curie-Weiss fit from 260 K to 290 K nearly matched with the theoretical resultant effective moment (6.24 μB) by considering Mn3+ ions in HS state and Ru5+ ions.Specific heat measurements revealed no long-range magnetic ordering down to 2 K, further suggesting the role of cationic disorder in the magnetic behaviour of Sr2MnRuO6.

Nonequivalent Antiferromagnetically Coupled Sublattices Induce Two-Step Spin-Crossover Transitions: Equilibrium and Nonequilibrium Aspects

As a continuation to the previously published work (Yalçın et al. (2022)), we investigate the equilibrium and nonequilibrium properties of the spin-crossover systems, with a specific focus on the nonequivalent sublattice, and compare these properties with those of the equivalent sublattices. We used the lowest approximation of the cluster variation method (LACVM) to derive the static equations for the order parameters of the two sublattices and determine high-spin fraction in relation to temperature and external magnetic field in a spin-crossover system. At a low temperature, the transition from stable high-spin (HS) state where nHS=1 occurs in the plateau region, where nHS=0.5 for nonequivalent sublattices. The order parameters for non-equivalent sublattices exhibit different states at the transition temperature. Also, we study the nonequilibrium properties of the order parameters and high-spin fraction using the path probability method (PPM). With the current model, we obtain and analyze the relaxation curves for the order parameters Sa, Sb, and high-spin fraction. These curves demonstrate the existence of bistability at low temperatures. At the end of this study, we present the flow diagram that shows the order parameters for different temperature values. The diagram exhibits states that are stable, metastable, and unstable.

Mononuclear Fe(III) Schiff Base Complex with Trans-FeO4N2 Chromophore of o-Aminophenol Origin: Synthesis, Characterisation, Crystal Structure, and Spin State Investigation

A new iron(III) complex (Et3NH)2[Fe(L)2](ClO4)·MeOH (1) where H2L = 2-{(E)-[2-hydroxyphenyl)imino]methyl}phenol has been synthesised and characterised by single crystal XRD, elemental analysis and DC magnetic susceptibility measurements. The dianionic ligands L2− coordinate in a tridentate fashion with the Fe(III) through their deprotonated phenolic oxygens and azomethine nitrogen atoms, resulting in a trans-FeO4N2 chromophore. Variable-temperature magnetic measurements were performed between 300 and 5 K under an applied field of 0.1 T and show that 1 is in the high spin state (S = 5/2) over the whole measured temperature range. This is confirmed by Mössbauer spectroscopy at 77 and 300 K.

Enhanced Oxygen Evolution and Zinc-Air Battery Performance via Electronic Spin Modulation in Heterostructured Catalysts.

Beyond optimizing electronic energy levels, the modulation of the electronic spin configuration is an effective strategy, often overlooked, to boost activity and selectivity in a range of catalytic reactions, including the oxygen evolution reaction (OER). This electronic spin modulation is frequently accomplished using external magnetic fields, which makes it impractical for real applications. Herein, spin modulation is achieved by engineering Ni/MnFe2O4 heterojunctions, whose surface is reconstructed into NiOOH/MnFeOOH during the OER. NiOOH/MnFeOOH shows a high spin state of Ni, which regulates the OH- and O2 adsorption energy and enables spin alignment of oxygen intermediates. As a result, NiOOH/MnFeOOH electrocatalysts provide excellent OER performance with an overpotential of 261 mV at 10 mA cm-2. Besides, rechargeable zinc-air batteries based on Ni/MnFe2O4 show a high open circuit potential of 1.56 V and excellent stability for more than 1000 cycles. This outstanding performance is rationalized using density functional theory calculations, which show that the optimal spin state of both Ni active sites and oxygen intermediates facilitates spin-selected charge transport, optimizes the reaction kinetics, and decreases the energy barrier to the evolution of oxygen. This study provides valuable insight into spin polarization modulation by heterojunctions enabling the design of next-generation OER catalysts with boosted performance.

Reduced internal stress of quasi-single crystalline Na4Fe3(PO4)2P2O7 electrode enhancing sodium-ion kinetics

A NASICON-type quasi-single crystalline Na4Fe3(PO4)2P2O7 (SC) cathode material was successfully synthesized via a freeze-drying method. The as-optimized SC sample displays both outstanding rate performance (107.9 and 88.5 mAhg−1 at 0.1C and 5C, respectively) and excellent cycling stability (88.1 % of capacity retention after 1000 cycles at 1C). Reduced sodium ion migration path of as-prepared SC cathode material effectively enhanced the kinetics of Na+ upon cycling. More importantly, the SC structure could suppress nearly 50 % of internal strain, prodigiously reducing the local stress accumulation accompanied by the inhomogeneous sodium concentration gradient during the charging/discharging processes. The smaller the stress accumulation, the more stable the crystal structure would be obtained, which maintained a more superb mechanical stability of the SC cathode material. At the same time, a high-spin state of Fe in the SC sample was confirmed by both of electron paramagnetic resonance and temperature-dependent magnetization susceptibility, indicating that the eg orbital occupation of Fe2+ could be regulated to optimize the bond strength between the reduction and oxidation processes. As a consequence, the band gap of SC material has decreased from 1.66 to 1.45 eV, and the electronic conductivity has increased from 6.0 to 32.4 μS/cm. It is believed that the SC cathode material could be a competitive candidate material for sodium ion batteries.

The role of Cu doped Ba0.5Sr0.5Fe0.95Zr0.05O3-δ: Local structure distortion, conductivity, and magnetization

The composition Ba0.5Sr0.5Fe1-xCuxZr0.05O3-δ (BSFCZ-x, x = 0–0.20) was successfully synthesized by the sol-gel self-combustion method using citric acid as fuel combustion. Structure, local structure, electrical, and magnetic properties are investigated. The X-ray diffraction revealed the oxides exhibit a cubic structure (Pm3 m), and the lattice parameter increases with x. The X-ray absorption data are analyzed to determine the oxidation state of B site metal transition Fe and Cu through edge-energy E0 evaluation. Fe performs the oxidation states Fe3+ and Fe4+, similarly to Cu2+ and Cu3+. Furthermore, the pre-edge was analyzed to determine the spin state configuration of the 3d subshell. The local lattice distortion was evaluated through EXAFS, resulting in a distorted FeO6 octahedron elongated to the z-axis, inducing the Jahn-Teller effect. The nonstoichiometric δ-value (3-δ) measurement leads to oxygen vacancy VO⦁⦁ defect. The electrical conductivity of semiconducting behavior increases significantly after Cu is dissolved in BSFZ up to 60 S/cm at 500 °C, from initially 5 S/cm. Furthermore, the magnetic properties show a slight magnetic saturation Ms for BSFZ related to the low spin state configuration of Fe 3d subshell, then significantly increased on BSFCZ samples due to Cu provoking spin state dragged partly to high spin state configuration.

Exploring annealing-triggered phase transformation, photoluminescence quenching, and synergistic effects of Co-doped TiO2 nanoparticles

This study investigates the influence of defects on the electronic, optical, and magnetic properties of tetragonal titanium dioxide (TiO2) and its cobalt-doped variant, Ti0.95Co0.05O2. The research findings of diffraction studies confirms the formation of phases such as anatase, rutile, and their combination within TiO2 nano-structures following annealing. The Debye-Scherrer's rings observed in the selected area electron diffraction patterns and transmission electron microscopy images showed an aggregate of randomly oriented nano-structures. Additionally, elemental analysis confirms the presence of Ti and O as primary constituents. The detailed analysis using microscopy and spectroscopy study identified a high-spin D2h state in Co2+, indicative of lattice defects across the TiO2 nano-structures. A blue shifting in the photoluminescence band gap emission peaks suggested the presence of oxygen vacancy defects in the doped nano-structures. Notably, the increased surface defects and reduced catalyst size promote rapid migration of electron-hole pairs to reaction sites i.e.; on the surface, thereby reducing recombination rates. Ultimately, the study concludes that anatase TiO2, due to its exceptional catalytic performance, is more favourable for applications in photo-catalysis and spintronics than its rutile or mixed-phase counterparts.