Magnetic Measurements Research Articles

Synthesis, physico-chemical properties, and AC induction heating of polycaprolactone-coated bio-compatible Fe3O4 nanoparticles

Ex-situ functionalization of Fe3O4 nanoparticles, synthesized using a coprecipitation method, with bio-compatible polycaprolactone (PCL) polymer is reported in this study. The formation of the crystalline structure of Fe3O4 is confirmed from the X-ray diffraction patterns. The presence of the PCL polymer on the surface of the coated MNPs is confirmed using Fourier transform infrared and X-ray photoelectron spectroscopy techniques and thermogravimetric analysis. Scanning and transmission electron microscopy imaging studies reveal the nearly spherical morphology of the synthesized nanoparticles. Room temperature magnetization measurements show the superparamagnetic nature of the PCL coated nanoparticles with high saturation magnetizations varying from ∼61–66 emu/g. Further, the room temperature coercivity is found to be reduced by ∼78 % for the PCL coated nanoparticles, which is attributed to the lowering of the interparticle interactions upon surface functionalization. Magnetic fluid hyperthermia studies on the PCL coated nanoparticles dispersed in ∼1 wt% agar gel shows significant alternating magnetic field induced heating efficiency, with temperature rise in the vicinity of the hyperthermia limit (∼42 °C). The highest specific absorption rate is found to be ∼85.4 ± 3.9 W/gFe, indicating an intrinsic loss power of ∼0.62 nHm2kg−1, which is significantly higher than the previously reported values for PCL coated Fe3O4 MNPs. The field induced heating efficiency is found to be correlated with the saturation magnetization of the PCL coated nanoparticles. In vitro cytotoxicity studies on human breast cancer (MCF-7) cell lines confirm the superior bio-compatibility of the PCL coated Fe3O4 nanoparticles. Superior field induced heating efficiency, coupled with good bio-compatibility makes the PCL functionalized Fe3O4 nanoparticles a potential candidate for magnetic fluid hyperthermia.

Dual-parameter fiber sensor based on Fabry-Pérot cavity cascaded with Terfenol-D rod integrated fiber Bragg grating

A kind of dual-parameter fiber sensor based on the Terfenol-D rod combined with the cascaded Fabry-Pérot interferometer-fiber Bragg grating (FPI-FBG) structure is demonstrated, which integrates the FBG with the Fabry-Pérot cavity made by fiber and polydimethylsiloxane (PDMS). The problem of temperature cross-sensitivity in magnetic field measurement is simply and ingeniously avoided. The experimental results show that the sensing system's temperature and magnetic field sensitivities are 121.56 pm/°C and 21.6 pm/mT, respectively. By using the dual-parameter matrix, the resolutions of temperature and magnetic field measurement are obtained to be 1.003 °C and 0.069 mT, respectively.

Single phase metamaterial behavior in [formula omitted] and [formula omitted] doped cobalt ferrites

This paper reports the characteristic properties of CoFe2O4(CFO), Co0.98Ag0.02Fe2O4(CAFO), and Co0.98Ti0.02Fe2O4(CTFO) spinel ferrites of Fd3‾m space group and grain size in the range of 160 – 170 nm. Fourier transform infrared spectra of these samples have revealed the metal-oxygen bands in the range of 448– 542 cm−1. Raman spectra have shown six distinct peaks corresponding to the mixed spinel structure, which have been used to calculate the cation distribution of the samples. The magnetic measurement at room temperature shows that after the doping of Ti4+ ions, the saturation magnetization increases from 47.70 to 66.68 emu/g, and coercivity decreases from 1.84 to 1.61 kOe, making the sample magnetically softer. The law of approach to saturation magnetization has been used to estimate the value of magneto crystalline anisotropy constant. The dielectric behavior of the samples has been thoroughly studied in this paper. The dielectric constant is positive below 300 °C; its value is comparable for CFO and CAFO samples but higher for CTFO. Above this temperature, the samples show an uncommon behavior of negative dielectric constant corresponding to the single phase metamaterial state and its value increases as temperature rises. This behavior can be interpreted with the help of Drude model of plasmonic resonance. The Nyquist plots change their properties from RC to RL type in this region. Such single phase metamaterials with negative dielectric constant could be useful for high temperature microwave applications.

Identifying Coronal Sources of L1 Solar Wind Disturbances Using the Fisk Heliospheric Magnetic Field and Potential Field Extrapolations during Three Solar Minima

The solar minima between solar cycles 22–23, 23–24, and 24–25 are the best observed minima on record. In situ solar wind and interplanetary magnetic field measurements by the Wind and ACE spacecraft at L1 with 1 hr cadence are explored using wavelet analyses for the most quiescent year during each minimum. Times of local peaks in periodicities are identified in the solar wind velocity, magnetic field components, and proton number densities. The measured radial velocities at these times are used to trace magnetic field lines to the photosphere using two models. The first is the Fisk heliospheric magnetic field that traces field lines from L1 to the photosphere. They connect exclusively to solar poles and in 88% of instances to locations of polar coronal holes (PCHs). The second model uses the Parker spiral to trace from L1 to the solar source surface and potential-field extrapolations from the source surface to the photosphere. These field lines terminate at equatorial and midlatitude coordinates, of which some are located close to coronal holes (CHs). This study connects for the first time CH signatures in the ecliptic plane at L1 with PCHs using the Fisk field. It shows how sources from both the solar equator and poles influence the solar wind at L1 and how the two models complement each other to identify these sources.

Mössbauer and magnetization measurements of multicomponent iron garnets

Four Gd-containing iron garnets were investigated using Mössbauer spectroscopy and Vibrating Sample Magnetometry over a wide temperature range, from 4K to ∼600K. The magnetic ordering temperature and hyperfine parameters determined on the basis of Mössbauer spectra for all samples were found to be surprisingly similar, differences were only noted for the average magnetic moments, which turned out to be strongly correlated with the magnetic moments of rare earth elements present in the structure. Further differences between the systems were also highlighted in measurements in the external 9T magnetic field, especially around the compensation temperature. Changes in the nature of the Mössbauer spectra were interpreted based on the crystal field approximation confirming the correctness of the interpretation of the temperature dependence of magnetization for these samples.

Multiple magnetic transition and magnetocaloric properties in the mixed valence Eu8CuNi2.5Si42.5 type I clathrate compound

We investigated the magnetocaloric and electrical transport properties of the Eu8CuNi2.5Si42.5 clathrate compound, synthesized by an arc melting and annealing method. X-ray photoemission spectroscopy revealed a mixed valence state of Eu2+ and Eu3+. The low-field and low-temperature magnetic measurements indicated a multiple magnetic transition, from ferromagnetic near 35 K to antiferromagnetic at 25 K. Increasing the magnetic field led to the broadening of antiferromagnetic peaks and a final ferromagnetic state under high magnetic fields, indicative of spin reorientation. The transition from a ferromagnetic to an antiferromagnetic state was further corroborated by specific heat measurements. We noted spontaneous magnetization at low temperatures via magnetic hysteresis and Arrott plot analysis. The coexistence of an antiferromagnetic ground state (attributed to the Eu2+ ions) and ferromagnetic clusters (associated with the Ni2+ ions) was supported by spontaneous magnetization at low temperatures in the antiferromagnetic state. The magnetocaloric analyses revealed a high spin entropy change over a broad temperature range for Eu8CuNi2.5Si42.5, which implies its potential as a robust low-temperature magnetocaloric material, distinguished by its high refrigerant capacity.

Fe3O4/CoFe2O4 core-shell nanoparticles with enhanced magnetic properties for hyperthermia application

Fe3O4/CoFe2O4 core/shell nanoparticles with varying shell thickness were fabricated by seed-mediated growth via thermal decomposition method. Ligand exchange process using poly(maleic anhydride-alt-1-octadecene) (PMAO) was performed to prepare the aqueous magnetic fluids from the as-synthesised nanoparticles. X-ray diffraction (XRD), transmission electron microscopy (TEM) and Quantum Design PPMS VersaLab were utilised to characterise morphological and magnetic properties of the sample. XRD results showed that all the particles were single phase with spinel structure and the average crystallite size in the range of 11–17 nm. All particles were spherical in TEM images with similar size compared to results calculated from XRD. Magnetic measurements were performed at different temperatures (50 − 300 K) at 30 kOe. The result showed that the saturation magnetisation (M s) and coercivity (H C) were significantly increased with the formation of hard magnetic shell with varying thickness. The dynamic light scattering (DLS) analysis presented a narrow distribution and zeta potential of −16 to −35 mV, indicating a good stability of the ferrofluids. The cytotoxicity of the FOC3/PMAO ferrofluid, which has the highest SAR value of 372.02 W g−1, was tested on Hep-G2 cell line at different concentrations from 10 to 100 μg ml−1. Less than 30% of the cell was inhibited, indicating that the FOC3/PMAO particles have low toxicity at these tested concentrations. Thus, these as-synthesised core/shell nanoparticles with uniform particle size, high saturation magnetisation, good stability and five-time increased specific absorption rate (SAR) compared to the Fe3O4 core nanoparticles are very promising in hyperthermia and magnetic resonance imaging (MRI) applications.

Spatiotemporal patterns of locus coeruleus integrity predict cortical tau and cognition.

Autopsy studies indicated that the locus coeruleus (LC) accumulates hyperphosphorylated tau before allocortical regions in Alzheimer's disease. By combining in vivo longitudinal magnetic resonance imaging measures of LC integrity, tau positron emission tomography imaging and cognition with autopsy data and transcriptomic information, we examined whether LC changes precede allocortical tau deposition and whether specific genetic features underlie LC's selective vulnerability to tau. We found that LC integrity changes preceded medial temporal lobe tau accumulation, and together these processes were associated with lower cognitive performance. Common gene expression profiles between LC-medial temporal lobe-limbic regions map to biological functions in protein transport regulation. These findings advance our understanding of the spatiotemporal patterns of initial tau spreading from the LC and LC's selective vulnerability to Alzheimer's disease pathology. LC integrity measures can be a promising indicator for identifying the time window when individuals are at risk of disease progression and underscore the importance of interventions mitigating initial tau spread.

Intersatellite Comparisons of GOES Magnetic Field Measurements

AbstractGOES‐16 and GOES‐17 are the first of NOAA's Geostationary Operational Environmental Satellite (GOES)‐R series of satellites. Each GOES‐R satellite has a magnetometer mounted on the end (outboard) and one part‐way down a long boom (inboard). This paper demonstrates the relative accuracy and stability of the measurements on a daily and long‐term basis. The GOES‐16 and GOES‐17 magnetic field observations from 2017 to 2020 have been compared to simultaneous magnetic field observations from each other and from the previous GOES‐NOP series satellites (GOES‐13, GOES‐14 and GOES‐15). These comparisons provide assessments of relative accuracy and stability. We use a field model to facilitate the inter‐satellite comparisons at different longitudes. GOES‐16 inboard and outboard magnetometers data suffer daily variations which cannot be explained by natural phenomena. Long‐term‐averaged GOES‐16 outboard (OB) data has daily variations of ±3 nT from average values with one‐sigma uncertainty of ±1.5 nT. Long‐term averaged GOES‐17OB magnetometer data have minimal daily variations. Daily average of the difference between the GOES‐16 outboard or GOES‐17 outboard measurements and the measurements made by another GOES satellite are computed. The long‐term averaged results show the GOES‐16OB and GOES‐17OB measurements have long‐term stability (±2 nT or less) and match measurements from magnetometers on other GOES within limits stated herein. The GOES‐17OB operational offset (zero field value) was refined using the GOES‐17 satellite rotated 180° about the Earth pointing axis (known as a yaw flip).

Non-destructive evaluation of the steel fibre content and anisometry in thin UHPFRC elements

The tensile response of ultra-high performance fibre-reinforced composites (UHPFRC) is decisive in many applications and depends on the steel fibre content and orientation. These vary troughout the structural element and may differ from those in the laboratory specimens used to characterize the material behaviour. This work presents the developments on a non-destructive test method based on the measurement of the magnetic inductance, substantiating its use for the determination of the fibre content and orientation in thin UHPFRC elements and allowing the estimation of the directionally dependent post-cracking tensile strength of the material in the structure. Starting from a probabilistic description of the fibre orientation, an existing physical model of the magnetic circuit composed of a U-shaped inductor and the composite is generalized and is used to derive the relations between the magnetic inductance measurements, the fibre volumetric fraction and the fibre orientation factor. A second-order tensor approximation of the relative magnetic permeability of the composite is proposed to determine the in-plane fibre orientation factor along any direction based on any three non-collinear measurements. Experimental evidence is presented supporting the theoretical developments. The factors that may affect the measurements are experimentally quantified. The paper concludes with an application example.

When the lava meets the sea: emplacement of the 2–4 ka San Bartolo lava flow field, Stromboli volcano (Italy)

When a lava flow enters a body of water, either a lake, sea, river or ocean, explosive interaction may arise. However, when it is an 'a'ā lava flow entering water, a more complex interaction occurs, that is very poorly described and documented in literature. In this paper, we analysed the 2–4 ka San Bartolo lava flow field emplaced on the north flank of Stromboli volcano, Italy. The lava flow field extends from ~ 650 m a.s.l. where the eruptive fissure is located, with two lava channels being apparent on the steep down to the coast. Along the coast the lava flow field expands to form a lava delta ~ 1 km wide characterised by 16 lava ‘Flow’ units. We performed a field survey to characterise the features of lava entering the sea and the associated formation of different components and magnetic measurements to infer the flow fabrics and emplacement process of the lava flow system. We measured the density, porosity and connectivity of several specimens to analyse the effect of lava-water interaction on the content in vesicles and their connectivity and conducted a macroscopic componentry analysis (clast count) at selected sites to infer the character of the eroded offshore segment of the lava flow field and its component flow units. The collected data allowed us to define the main components of a lava delta fed by 'a'ā lava flows, with its channels, littoral units, ramps, lava tubes, and inflated pāhoehoe flows controlled by the arterial 'a'ā flow fronts. The spatial organisation of these components allowed us to build a three-step descriptive model for 'a'ā entering a water. The initial stage corresponds to the entry of channel-fed 'a'ā lava flow into the sea which fragments to form metric blocks of 'a'ā lava. Continued lava supply to the foreshore causes flow units to stall while spreading over this substrate. Subsequent 'a'ā lava flow units ramp up behind the stalled flow front barrier. Lava tubes extending through the stalled flow barrier feed the seaward extension of a bench made of several pāhoehoe flow units.

Enhancement of Cobalt Bismuth Nano-Ferrite via Heat Treatment to be Applied in High-Frequency and Antimicrobial Applications

AbstractCobalt bismuth nano-ferrite (Co/Bi) with the chemical formula CoBi0.02Fe1.98O4 was produced using a simple flash auto-combustion method at three different temperatures: as-prepared, 600°C, and 800°C. A single-phase spinel structure was confirmed using X-ray diffraction, and the nano-scale morphology was examined using AFM (atomic force microscopy). Magnetic measurements demonstrated that increasing the annealing temperature increased the saturation magnetization Ms by 1.3 times. However, the coercivity Hc changed from semi-hard ferrite (as-prepared sample) to soft ferrite (Co/Bi nano-ferrite at 800°C) and reduced 10.7 times that of as-prepared nanoparticles. Therefore, the 800°C Co/Bi nano-ferrite with a low coercive field is recommended for transformers, recording heads, inductor cores, magnetic shielding, and microwave devices. The as-prepared sample and that at 600°C displayed super-high microwave frequency (SHF) in the X band in high-frequency applications calculated from magnetic measurement. The 800°C sample also has an extremely high microwave frequency in the Ku band, which is utilized in radar and satellite communications. Antimicrobial characterization showed that raising the annealing temperature increased the effectiveness of the samples against tested microorganisms. Thus, the samples under investigation are highly suggested for ultra-high microwave frequency applications and biological antibacterial nanomaterials.

Targeting Manganese Amidinates and ß-Ketoiminates Complexes as Precursors for Mn-Based Thin Film Vapor Deposition.

With a focus on Mn based organometallic compounds with suitable physico-chemical properties to serve as precursors for chemical vapor deposition (CVD) and atomic layer deposition (ALD) of Mn-containing materials, systematic synthetic approaches with ligand variation, detailed characterization, and theoretical input from density functional theory (DFT) studies are presented. A series of new homoleptic all-nitrogen and mixed oxygen/nitrogen-coordinated Mn(II) complexes bearing the acetamidinate, formamidinate, guanidinate and ß-ketoiminate ligands have been successfully synthesized for the first time. The specific choice of these ligand classes with changes in structure and coordination sphere and side chain variations result in significant structural differences whereby mononuclear and dinuclear complexes are formed. This was supported by density functional theory (DFT) studies. The compounds were thoroughly characterized by single crystal X-ray diffraction, magnetic measurements, mass spectrometry and elemental analysis. To evaluate their suitability as precursors for deposition of Mn-based materials, the thermal properties were investigated in detail. Mn(II) complexes possessing the most promising thermal properties, namely Bis(N,N´-ditertbutylformamidinato)manganese(II) (IV) and Bis(4-(isopropylamino)pent-3-en-2-onato)manganese(II) (ßIII) were used in reactivity studies with DFT to explore their interaction with oxidizing co-reactants such as oxygen and water which will guide future CVD and ALD process development.

PURA syndrome-causing mutations impair PUR-domain integrity and affect P-body association.

Mutations in the human PURA gene cause the neurodevelopmental PURA syndrome. In contrast to several other monogenetic disorders, almost all reported mutations in this nucleic acid-binding protein result in the full disease penetrance. In this study, we observed that patient mutations across PURA impair its previously reported co-localization with processing bodies. These mutations either destroyed the folding integrity, RNA binding, or dimerization of PURA. We also solved the crystal structures of the N- and C-terminal PUR domains of human PURA and combined them with molecular dynamics simulations and nuclear magnetic resonance measurements. The observed unusually high dynamics and structural promiscuity of PURA indicated that this protein is particularly susceptible to mutations impairing its structural integrity. It offers an explanation why even conservative mutations across PURA result in the full penetrance of symptoms in patients with PURA syndrome.

PURA syndrome-causing mutations impair PUR-domain integrity and affect P-body association

Mutations in the human PURA gene cause the neurodevelopmental PURA syndrome. In contrast to several other monogenetic disorders, almost all reported mutations in this nucleic acid-binding protein result in the full disease penetrance. In this study, we observed that patient mutations across PURA impair its previously reported co-localization with processing bodies. These mutations either destroyed the folding integrity, RNA binding, or dimerization of PURA. We also solved the crystal structures of the N- and C-terminal PUR domains of human PURA and combined them with molecular dynamics simulations and nuclear magnetic resonance measurements. The observed unusually high dynamics and structural promiscuity of PURA indicated that this protein is particularly susceptible to mutations impairing its structural integrity. It offers an explanation why even conservative mutations across PURA result in the full penetrance of symptoms in patients with PURA syndrome.

Coordination of N, O-donor Appended Schiff Base Ligand N, N’-bis (3-Methoxy Salicylidenimino-1,3-diaminopropane) towards Nickel (II), Copper (II) and Zinc (II) : Synthèses, Crystal Structure

New complexes prepared by the reaction of N,N’-bis(3-methoxysalicylidenimino-1,3-diaminopropane) (H2L) with Ni(II), Zn(II) and Cu(II) ions are reported in this paper. The H2L ligand is structurally characterized by elemental analysis, NMR, infrared, UV-Vis spectroscopies, conductance and magnetic room temperature measurement. The mononuclear complex of Ni(II) (C19H24N2NiO6) is characterized by single X-ray diffraction. The compound crystallizes in the orthorhombic system in the space group Pnma with the unit cell parameters a = 7.3754(5) Å, b = 21.9576(13) Å, c = 11.5546(6) Å, α = 90°, β = 90°, γ = 90° The ligand H2L acts in tetradentate fashion in its di-deprotonated form. Two coordinated water molecules complete the coordination sphere. The environment around the Ni(II) center is best described as an octahedral geometry.

Manipulating Single‐Molecule Exciplex TADF and Deep‐Blue RTP Through Non‐Covalent π–π Interaction in a Molecular Foldamer

AbstractAlthough the π–π stacking has been widely applied for constructing aggregated emitters in optoelectronics fields, the role of intramolecular non‐covalent π–π interactions has not been well studied. Here, a supramolecular foldermer M‐σ‐C, with the electron donor (D) and acceptor (A) units spatially separated with a non‐covalent bond at a close distance by methylene linker is designed and synthesized. This gives a face‐to‐face D/A stacking configuration with supramolecular π–π interactions. Temperature‐dependent nuclear magnetic resonance measurements and single crystal analyses confirm its folding configuration. In solutions, M‐σ‐C exhibits a single‐molecule exciplex thermally activated delayed fluorescence (TADF) property ascribing to the efficient intramolecular through‐space charge transfer (CT) process. While single‐molecule deep‐blue room temperature phosphorescence (RTP) with a long afterglow lifetime of 236 ms is observed in a nonpolar matrix, which represents the record lifetime among current 3CT‐character featured RTP. This work indicates that intramolecular non‐covalent interactions play an important role in manipulating high‐performance single‐molecule exciplex TADF and RTP, and provide a feasible molecular design strategy for supramolecular chemistry involving the development of optoelectronic materials.

Unusual Stabilisation of Remarkably Bent Tetra-Cationic Tetra-radical Intermolecular Fe(III) μ-Oxo Tetranuclear Complexes.

A hitherto unknown series of air stable, π-conjugated, remarkably bent tetra-cation tetra-radical intermolecular Fe(III) μ-oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X-ray structure determination of two such molecules. These species facilitate long-range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six-coordinate iron centres stabilise the admixed intermediate spin states while the central five-coordinate iron centres stabilise the high-spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)-O-Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π-cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

β-Phase Yb5Sb3Hx: Magnetic and Thermoelectric Properties Traversing from an Electride to a Semiconductor.

An electride is a compound that contains a localized electron in an empty crystallographic site. This class of materials has a wide range of applications, including superconductivity, batteries, photonics, and catalysis. Both polymorphs of Yb5Sb3 (the orthorhombic Ca5Sb3F structure type (β phase) and hexagonal Mn5Si3 structure type (α phase)) are known to be electrides with electrons localized in 0D tetrahedral cavities and 1D octahedral chains, respectively. In the case of the orthorhombic β phase, an interstitial H can occupy the 0D tetrahedral cavity, accepting the anionic electron that would otherwise occupy the site, providing the formula of Yb5Sb3Hx. DFT computations show that the hexagonal structure is energetically favored without hydrogen and that the orthorhombic structure is more stable with hydrogen. Polycrystalline samples of orthorhombic β phase Yb5Sb3Hx (x = 0.25, 0.50, 0.75, 1.0) were synthesized, and both PXRD lattice parameters and 1H MAS NMR were used to characterize H composition. Magnetic and electronic transport properties were measured to characterize the transition from the electride (semimetal) to the semiconductor. Magnetic susceptibility measurements indicate a magnetic moment that can be interpreted as resulting from either the localized antiferromagnetically coupled electride or the presence of a small amount of Yb3+. At lower H content (x = 0.25, 0.50), a low charge carrier mobility consistent with localized electride states is observed. In contrast, at higher H content (x = 0.75, 1.0), a high charge carrier mobility is consistent with free electrons in a semiconductor. All compositions show low thermal conductivity, suggesting a potentially promising thermoelectric material if charge carrier concentration can be fine-tuned. This work provides an understanding of the structure and electronic properties of the electride and semiconductor, Yb5Sb3Hx, and opens the door to the interstitial design of electrides to tune thermoelectric properties.

Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes

AbstractA hitherto unknown series of air stable, π‐conjugated, remarkably bent tetra‐cation tetra‐radical intermolecular Fe(III) μ‐oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X‐ray structure determination of two such molecules. These species facilitate long‐range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six‐coordinate iron centres stabilise the admixed intermediate spin states while the central five‐coordinate iron centres stabilise the high‐spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)−O−Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π‐cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.