Large Quadrupole Splitting Research Articles

Electronic and magnetic phase diagram of Sr2FeO4 at high pressure: A synchrotron Mössbauer study

Transition metal (TM) oxides with high oxidation state TM ions exhibit a variety of unconventional electronic and magnetic states owing to electron correlations effects combined with highly covalent TM–O bonding. Here, we have studied the pressure dependence of electronic state and magnetism of the K2NiF4-type iron(IV) oxide Sr2FeO4 up to 89 GPa by temperature and magnetic field dependent energy-domain synchrotron Mössbauer spectroscopy and derived a (P,T) magnetic phase diagram. Considering also previous resistance studies [Rozenberg , ] several magnetic and electronic regimes with increasing pressure can be identified. Near 7 GPa, the insulating cycloidal antiferromagnetic low-P state is transformed into a semiconducting ferromagnetic state and the magnetic ordering temperature Tm increases from 55 K at ambient pressure to about 100 K at 13 GPa. Between 18 and about 50 GPa the system is ferromagnetic and metallic (FMM) with a strong rise of Tm to above room temperature (RT). Contrary to a recent theoretical study [Kazemi-Moridani , ], the FMM state is attributed to a high-spin t2g3eg1 electronic state with itinerant eg coupled to more localized t2g electrons. Between 50 and 89 GPa a doublet with large quadrupole splitting in the RT Mössbauer spectra indicates a partial high-spin to low-spin (t2g4) transition leading to a decrease in Tm again. The general features of the (P,T) phase diagram of Sr2FeO4 are comparable to those of other simple and A-site ordered iron(IV) perovskite-related oxides with the peculiarity that Sr2FeO4 adopts an insulating state without charge disproportionation of Fe4+ in the low-P region. The high-pressure behavior of Sr2FeO4 and other iron(IV) oxides may be relevant for exploring the role of Hund's physics in multiorbital systems and contributing to the understanding of the electronic situation in unconventional superconductors such as La3Ni2O7 and Sr2RuO4. Published by the American Physical Society 2024

How Does a Heme Carbene Differ from Diatomic Ligated (NO, CO, and CN-) Analogues in the Axial Bond?

Compared to well studied diatomic ligands (NO, CN-, CO), the axial bonds of carbene hemes is much less known although its significance in biological chemistry. The unusually large quadrupole splitting (Δ EQ = +2.2 mm·s-1) and asymmetric parameter (η = 0.9) of the five-coordinate heme carbene [Fe(TTP)(CCl2)], which is the largest among all known low spin ferrohemes, has driven investigations by means of Mössbauer effect Nuclear Resonance Vibrational Spectroscopy (NRVS). Three distinct measurements on one single crystal (two in-plane and one out-of-plane) have demonstrated comprehensive vibrational structures including stretch (429) and bending modes (472 cm-1) of the axial Fe-CCl2, and revealed iron vibrational anisotropy in three orthogonal directions for the first time. Frontier orbital analysis especially comparisons with diatomic analogues (NO, CN-, CO) suggest that CCl2, similar to NO, has led to strong but anisotropic π bonding in a ligand-based "4C"-coordinate which induced the vibrational anisotropies and very large Mössbauer parameters. This is contrasted to CN- and CO complexes which possess a porphyrin-based "4N"-coordinate electronic and vibrational structures due to inherent on-axis linear ligation.

Synthesis and Electronic Ground-State Properties of Pyrrolyl-Based Iron Pincer Complexes: Revisited.

The pyrrolyl-based iron pincer compounds [(tBuPNP)FeCl] (1), [(tBuPNP)FeN2] (2), and [(tBuPNP)Fe(CO)2] (3) were prepared and structurally characterized. In addition, their electronic ground states were probed by various techniques including solid-state magnetic susceptibility and zero-field 57Fe Mössbauer and X-band electron paramagnetic resonance spectroscopy. While the iron(II) starting material 1 adopts an intermediate-spin (S = 1) state, the iron(I) reduction products 2 and 3 exhibit a low-spin (S = 1/2) ground state. Consistent with an intermediate-spin configuration for 1, the zero-field 57Fe Mössbauer spectrum shows a characteristically large quadrupole splitting (ΔEQ ≈ 3.7 mm s-1), and the solid-state magnetic susceptibility data show pronounced zero-field splitting (|D| ≈ 37 cm-1). The effective magnetic moments observed for the iron(I) species 2 and 3 are larger than expected from the spin-only value and indicate an incompletely quenched orbital angular momentum and the presence of spin-orbit coupling in the ground state. The experimental findings are complemented by density functional theory computations, which are in good agreement with the experimental data. Most notably, these calculations reveal a low-lying (S = 2) excited state for complex 1; furthermore, the computed Mössbauer parameters for all complexes studied herein are in excellent agreement with the experimental findings.

Electronic Configuration and Ligand Nature of Five-Coordinate Iron Porphyrin Carbene Complexes: An Experimental Study.

The five-coordinate iron porphyrin carbene complexes [Fe(TPP) (CCl2)] (TPP = tetraphenylporphyrin), [Fe(TTP) (CCl2)] (TTP = tetratolylporphyrin) and [Fe(TFPP) (CPh2)] (TFPP = tetra(pentafluorophenyl)porphyrin), utilizing two types of carbene ligands (CCl2 and CPh2), have been investigated by single crystal X-ray, XANES (X-ray absorption near edge spectroscopy), Mössbauer, NMR and UV-vis spectroscopies. The XANES suggested the iron(II) oxidation state of the complexes. The multitemperature and high magnetic field Mössbauer experiments, which show very large quadrupole splittings (QS, ΔEQ), determined the S = 0 electronic configuration. More importantly, combined structural and Mössbauer studies, especially the comparison with the low spin iron(II) porphyrin complexes with strong diatomic ligands (CS, CO and CN-) revealed the covalent bond nature of the carbene ligands. A correlation between the iron isomer shifts (IS, δ) and the axial bond distances is established for the first time for these donor carbon ligands (:C-R).

Crystallograhic and magnetic properties of Fe1−x Ni x Ga2O4

We report the crystallographic and magnetic effects on inverse spinel Fe1−xNixGa2O4 (0.0 ≤ x ≤ 0.9) due to doped Ni cations. The crystalline structures of Fe1−xNixGa2O4 (0.0 ≤ x ≤ 0.9) were examined by using a Philips X’Pert diffractometer with a Cu Kα radiation (λ = 1.5406 A) source and analyzed with the Rietveld refinement method. The crystal structures were found to be inverse spinel with space group Fd-3m. From the Rietveld analysis, with increasing Ni concentration, the ratio of magnetic Fe2+ cations, compared to the total number of Fe2+ cations on A-site (tetrahedron) decreased from 43 to 7%, and that on B-site (octahedron) increased from 57 to 93%. The lattice constants a0, and bond length \(d_{Ga^{3+}-Fe^{2+}[Ni^{2+}]}\) on A-site and B-site decreased linearly with increasing Ni concentration. From the temperature dependence of susceptibility χ in zero-field-cooled and field-cooled magnetization under 400 Oe, with increasing Ni concentration, the sample showed a decrease in the freezing temperature Tf. Mossbauer spectra of all samples at room temperature showed 2-sets (A-site, and B-site) with large electric quadrupole splitting. The Mossbauer absorption area ratio of A-site decreased, while that of B-site increased with increasing Ni concentration, which is accord with the Rietveld refinement analysis of the XRD results.

Synchrotron-based Nickel Mössbauer Spectroscopy.

We used a novel experimental setup to conduct the first synchrotron-based (61)Ni Mössbauer spectroscopy measurements in the energy domain on Ni coordination complexes and metalloproteins. A representative set of samples was chosen to demonstrate the potential of this approach. (61)NiCr2O4 was examined as a case with strong Zeeman splittings. Simulations of the spectra yielded an internal magnetic field of 44.6 T, consistent with previous work by the traditional (61)Ni Mössbauer approach with a radioactive source. A linear Ni amido complex, (61)Ni{N(SiMe3)Dipp}2, where Dipp = C6H3-2,6-(i)Pr2, was chosen as a sample with an "extreme" geometry and large quadrupole splitting. Finally, to demonstrate the feasibility of metalloprotein studies using synchrotron-based (61)Ni Mössbauer spectroscopy, we examined the spectra of (61)Ni-substituted rubredoxin in reduced and oxidized forms, along with [Et4N]2[(61)Ni(SPh)4] as a model compound. For each of the above samples, a reasonable spectrum could be obtained in ∼1 d. Given that there is still room for considerable improvement in experimental sensitivity, synchrotron-based (61)Ni Mössbauer spectroscopy appears to be a promising alternative to measurements with radioactive sources.

Single-crystal neutron diffraction and Mössbauer spectroscopic study of hureaulite, (Mn,Fe)5(PO4)2 (HPO4)2 (H2O)4

The crystal chemistry of hureaulite from the Jocao (Cigana) pegmatite, Conselheiro Pena, Doce Valley, Minas Gerais (Brazil), was investigated by electron microprobe analysis in wavelength-dispersive mode, single-crystal Laue (at 293 K) and monochromatic neutron diffraction (at 2.3 K), and 57 Fe-Mossbauer spectroscopy [ M(1),M(2),M(3) (Mn 2+ 3.61 Fe 2+ 1.21 Ca 0.11 Mg 0.03 ) ∑=4.96 ( P(2) (PO 4 ) 2 (H 1.04 P(1) PO 4 ) 2 (H 2 O) 3.92 , Z = 4, a = 17.603(6), b = 9.087(2), c = 9.404(4) A, β = 96.66(4)°, and V = 1494.1(9) A 3 at 293 K, space group C 2 /c ]. The neutron refinements confirm the general structure model previously reported, showing that five independent H sites (with full site occupancy) occur in the hureaulite structure, one of them as member of the unique hydroxyl group ( i.e. , O(1)-H(1) ) and the other four belonging to two independent H 2 O molecules ( i.e. , H(2)-O(9)-H(3) and H(4)-O(10)-H(5) ). The hydroxyl group is the vertex of one of the two independent P-tetrahedra ( i.e. , HOPO 3 ), whereas the two H 2 O molecules are the vertices of the (Mn,Fe)-octahedra. No zeolitic H 2 O occurs in hureaulite structure. The complex hydrogen bonding scheme in hureaulite is now well defined, with five hydrogen bonds energetically favorable. The element distribution among the octahedral sites, deduced on the basis of the neutron structure refinements, shows that the highest fraction of Fe populates the M(2) site (~36%), whereas lower fractions are observed at M(1) and M(3) ( i.e. , ~13–15 and 11–12%, respectively). The 57 Fe Mossbauer spectrum of hureaulite confirms the absence of ferric iron in the sample. The spectrum shows four well-separated absorption lines which are best fitted with three doublets. The well-resolved doublet (with the largest quadrupole splitting) is here assigned to the M(3) site, in line with the pronounced preference of Mn 2+ for the M(3) site as shown by the neutron structure refinements. The two innermost doublets have almost identical isomer shifts, though with slightly different quadrupole splitting values; the smaller quadrupole splitting value is assigned to the M(2) site, which is expected to have a slightly lower polyhedral distortion than the M(1) site, according to the experimental findings based on the neutron refinements.

Recoil-free fractions of iron in aluminous bridgmanite from temperature-dependent Mössbauer spectra

Aluminous bridgmanite (Al-Bm) is the dominant phase in the Earth’s lower mantle. In this study, the Mossbauer spectra of an Al-Bm sample Mg0.868Fe0.087Si0.944Al0.101O2.994 were recorded from 65 to 300 K at 1 bar. The temperature dependence of the center shift was fitted by the Debye model and yielded the Debye temperatures of 305 ± 3 K for Fe2+ and 361 ± 22 K for Fe3+. These values are lower than those of Al-free bridgmanite by 17 and 24%, respectively, indicating that the presence of Fe and Al increases the average Fe-O bond length and weakens the bond strength. At 300 K, the calculated recoil-free fractions of Fe2+ (0.637 ± 0.006) and Fe3+ (0.72 ± 0.02) are similar and therefore the molar fractions of Fe2+ and Fe3+ are nearly the same as the area fractions of the corresponding Mossbauer doublets. At 900 K, the calculated recoil-free fractions of Fe3+ is 46% higher than that of Fe2+, implying that the molar fraction of Fe3+ is only 41% for a measured spectral area fraction of 50%, and that the area fractions of iron sites may change with temperature without any changes in the valence state or spin state of iron. We infer that Fe3+ accounts for 46 ± 2% of the iron in the Al-Bm and it enters the A site along with Al3+ in the B site through the coupled-substitution mechanism. An Fe2+ component with large quadrupole splitting (~4.0 mm/s) was observed at cryogenic conditions and interpreted as a high-spin distorted iron site.

Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6'-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer.

Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [H2bipy(ttr)2] in the presence of Fe(II) in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2](-) and [bipy(ttr)2](2-) embrace the Fe(II) centers defining discrete molecular units 1 with the Fe(II) ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the Fe(II) is high-spin, and its Mössbauer spectrum is characterized by a relatively large average quadrupole splitting, ΔEQ = 3.42 mm s(-1). Compound 2 defines a strongly distorted octahedral environment for Fe(II) in which one [bipy(ttr)2](-) anion coordinates the equatorial positions of the Fe(II) center, while the axial positions are occupied by peripheral N-tetrazole atoms of two adjacent {Fe[bipy(ttr)2]}(0) moieties thereby generating an infinite double-layer sheet. Compound 2 undergoes an almost complete spin crossover transition between the high-spin and low-spin states centered at about 221 K characterized by an average variation of enthalpy and entropy ΔH(av) = 8.27 kJ mol(-1), ΔS(av) = 37.5 J K(-1) mol(-1), obtained from calorimetric DSC measurements. Photomagnetic measurements of 2 at 10 K show an almost complete light-induced spin state trapping (LIESST) effect which denotes occurrence of antiferromagnetic coupling between the excited high-spin species and TLIESST = 52 K. The crystal structure of 2 has been investigated in detail at various temperatures and discussed.

57Fe Mössbauer study of a secondary phase in FeSe1−x with a large quadrupole splitting

We have studied the hyperfine interactions in samples belonging to the Fe-Se system. Several samples with various concentrations of selenium were synthesized and investigated. The objective was to find synthesis conditions increasing the concentration of a secondary Fe-Se phase with a rather large quadrupole splitting of ~1.7 mm/s. At Tm ≈ 104 K this secondary phase undergoes a magnetic ordering.

Mössbauer study of oxo derivatives of iron in the Fe2O3-Na2O2 system

Various compositions of oxo derivatives of iron reacting with sodium peroxide have been studied by Mossbauer spectroscopy. We have examined several mathematical models of the measured spectra. The results obtained are inconsistent with hypotheses made previously that such conditions may lead to the formation of compounds of iron in oxidation states above (6+). We demonstrate that a large excess of an alkali peroxide leads, most likely, to the formation of at least two iron(V) derivatives in tetrahedral coordination. In their Mossbauer spectra, they have isomer shifts of −0.45 and −0.51 mm/s and unusually large quadrupole splittings: 1.32 and 1.94 mm/s (at room temperature).

Multiple Metal–Metal Bonds in Iron–Chromium Complexes

Mix and match: The first structural examples of MM multiple bonds between different first-row transition metals are elucidated using X-ray crystallography (see picture; Fe pink, Cr green, P yellow, N blue), spectroscopic methods, and calculations. The FeCr bonds are ultrashort (<2 Å) with highly delocalized σ and π bonds and unusually large quadrupole splittings in Mössbauer spectroscopy.

Spin-Disorder and Non-Degenerate Energy States in Geometrically Frustrated Materials

We have studied chalcogenide Ni <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">1-x</sub> Fe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">x</sub> Ga <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> S <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> , showing geometrical frustration effect. M-H curves at 4.2 K reveal that the disordered spins cannot be rotated completely along the direction of high external field of 5 T, since these spins are strongly constrained in the triangular lattice. H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">C</sub> increases with increasing Fe concentration, being consistent with the enhanced antiferromagnetic (AFM) spin-spin interactions and the suppressed spin-fluctuation due to the increase in freezing temperature T <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">f</sub> . The specific heat (C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">P</sub> /T) measurement do not show any phase transformation between 2 and 160 K and there is no clear indication of gap in the temperature dependent C <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">P</sub> curve between 0 and 7 T, because the atomic short-range ordering of the strained spin in the geometrically frustrated triangular lattice exists at low temperature. Though typical geometrically frustrated magnet shows degeneracy, Mossbauer analysis at 4.2 K shows that 5D of 3d orbit in the samples studied here is splitted into <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sup> T <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2g</sub> and <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sup> E <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2g</sub> , and <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">5</sup> T <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2g</sub> is further splitted into singlet and doublet by large electric quadrupole splitting. This suggests that Fe <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> ionic state has no absolute degenerate energy states in all samples due to Jahn-Teller effect.

Mössbauer spectroscopy of Pb-bearing minerals from the jarosite group

The minerals of the jarosite group, including the jarosite-beudantite-segnitite and jarosite-beaverite-osarizawaite isomorphic series, were studied with Mossbauer spectroscopy. All the samples were collected from the oxidation zones of the South Urals sulfide deposits. In contrast to the jarosite containing one Fe3+ doublet in the Mossbauer spectrum, the Pb-bearing members of the jarosite group—beudantite and beaverite—have two doublets in their spectra. Fe3+ is distributed at two sites with similar isomer shifts and different quadrupole splitting. The quantitative ratio of those doublets in the structure is roughly equal. The Mossbauer spectra of the intermediate jarosite-beudantite and beaverite-osarizawaite members are superpositions of the jarosite and beudantite spectrum types with a prevalent jarosite doublet and larger quadrupole splitting. An admixture of antimony increases the Fe3+ content in the doublet with smaller quadrupole splitting. The unequal Fe3+ distribution in those two sites may be related to the ordering of cations in octahedrons. The appearance of two different Fe3+ sites probably resulted from the local coordinating role of Pb rather than from isomorphic replacement in anion groups.

Synthesis and Characterization of Di- and Tetracarbene Iron(II) Complexes with Chelating N-Heterocyclic Carbene Ligands and Their Application in Aryl Grignard–Alkyl Halide Cross-Coupling

A series of new and known bis(imidazolium) chloride and bromide salts bridged by either a methylene group (1–8, 10a,b) or an ethylene group (9a,b) and bearing different N substituents (Me, Et, Bn, tBu, Mes) have been reacted with [Fe{N(SiMe3)2}2]2 to yield the four-coordinate iron(II) complexes [LFeX2] (11–20; X = Cl, Br; L = chelating bis(imidazolylidene) ligand). Molecular structures of six of these complexes have been characterized by X-ray crystallography, and selected examples have been characterized by 1H NMR and UV–vis spectroscopy, cyclic voltammetry, Mossbauer spectroscopy, and SQUID magnetometry. In all cases the iron(II) is found in a distorted-tetrahedral environment; it is in the high-spin state and shows large quadrupole splittings in the range 3.67–4.03 mm·s–1 (δ = 0.73–0.81 mm·s–1). Subtleties of the metric parameters depend on the bridging unit between the two imidazolylidene groups, the peripheral N substituents, and the coligand (Cl or Br). In case of rather small (Me, Et) or flexible (...

Mössbauer studies of subfossil oak

Subfossil oak wood found in a dried-up bog in Bavaria, Germany, was studied by Mossbauer spectroscopy. The bog oaks contain substantial amounts of iron taken up from the bog waters and presumably forming complexes with the tanning agents in the oak wood. The iron is mainly Fe3 + and much of this exhibits an uncommonly large quadrupole splitting of up to 1.6 mm/s that can tentatively be explained by the formation of oxo-bridged iron dimers. Only rarely, mainly in the dense wood of the roots of bog oaks, was divalent iron found. When the wood was ground to a powder the divalent iron oxidized to Fe3 + within hours. This suggests that iron is taken up from the bog water as Fe2 + and oxidizes only when the wood emerges from the water and comes into contact with air.

Synthesis and Characterization of New Iron(III) Layered Hydroxides

A new layered iron hydroxide was synthesized by a wet chemical technique, by which aqueous ferrous sulfate solution was gradually oxidized by using sodium carbonate at 283∼333 K. Obtained yellowish precipitates identified by X-ray powder diffraction had a similar structure to the layered double hydroxides. The observed interlayer spacing was about d=0.74 nm. Electron micrographs showed that the particle had plate-like morphology. Electron diffraction pattern of the plate-like particles had hexagonal symmetry, when the electron beam was aligned normal to the planes. Mossbauer spectrum suggested that all iron ions were paramagnetic Fe3+ states with large quadrupole splittings at room temperature. These results show that the obtained new layered iron hydroxide cotains only Fe(III) ion species. Water vapor adsorption curves of the sample oxidized at 291 K showed high adsorption value (19 wt%) by unit weight.

Mössbauer study on the polar ferrimagnet GaFeO3

In order to clarify the origin of magnetoelectric (ME) effect in the polar ferrimagnet GaFeO3, we have conducted Mössbauer spectroscopy by using a stoichiometric single crystal. The spectra are composed of three subspectra, corresponding to Fe3+ ions on Fe1, Fe2, and Ga2 sites. The quadrupole splitting (QS) of Fe1 subspectrum, 1.05mm/s, is too large to be explained by the electric field gradients (EFG) due to the lattice contribution. At 5K, there is no difference in the quadrupole parameters between the spectrum with and without applied magnetic field, suggesting that the ME effect is not caused by a displacement of ions. Note that in applied magnetic field, Fe1 subspectrum shows extra increase in observed field of about 10kOe. In conjunction with the large QS, this feature may be due to the spin-orbit interaction, which can also be the cause of the large magnetic anisotropy.

Electron-nuclear double resonance study of [formula omitted] ions in [formula omitted] crystals

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify and characterize V 4+ ions in a bulk single crystal of vanadium dioxide (V O 2). These S = 1 / 2 defects are observed in the as-grown crystal because an adjacent nonmagnetic M 4+ impurity, e.g., a Si 4+ ion, has destroyed the normal antiferromagnetic coupling associated with the close pairs of V 4+ ions that occur in the low-temperature monoclinic phase of V O 2. EPR spectra taken near 5 K with the magnetic field along the [110] and [001] axes show resolved hyperfine patterns due to one 51V nucleus. ENDOR spectra taken at 5 K with the magnetic field parallel to the [001] axis have large nuclear electric quadrupole splittings as a result of a significant electric field gradient at the 51V nucleus. Spin-Hamiltonian parameters describing the electron Zeeman, hyperfine, and nuclear electric quadrupole interactions are reported.

Characterization of Three Members of the Electron‐Transfer Series [Fe(pda)2]n (n=2−, 1−, 0) by Spectroscopy and Density Functional Theoretical Calculations [pda=Redox Non‐innocent Derivatives of N,N′‐Bis(pentafluorophenyl)‐o‐phenylenediamide(2−, 1.−, 0)

The four-coordinate iron complexes, [Fe(III)(pda(2-))(pda(.-))] (1) and [AsPh(4)](2)[Fe(II)(pda(2-))(2)] (2) were synthesized and fully characterized; pda(2-) is the closed-shell ligand N,N'-bis(pentafluorophenyl)-o-phenylenediamido(2-), and pda(.-) represents its one-electron-oxidized pi-radical anion. Single-crystal X-ray diffraction studies of 1 and 2 performed at 100(2) K reveal a distorted tetrahedral coordination environment at the iron centers, as a result of the intramolecular pi-pi interactions between C(6)F(5) rings. The electronic structures of 1 and 2 were unambiguously determined by a combination of (57)Fe Mössbauer and electronic spectroscopy, magnetic susceptibility measurements, X-ray crystallography, and DFT calculations. Compound 1 contains an intermediate-spin Fe(III) ion (S(Fe)=3/2) strongly antiferromagnetically coupled to a pi-ligand radical (S(R)=1/2) yielding an S(t)=1 ground state. Complex 2 possesses a high-spin Fe(II) center (S(Fe)=2) with two closed-shell dianionic ligands. Complexes 1 and 2 are members of the redox series [Fe(pda)(2)](n) with n=0 for 1 and n=2- for 2. The anion n=1- has been reported previously in the coordination salt [Fe(dad)(3)][Fe(pda)(2)] (3; dad=N,N'-bis(phenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene). A complicated temperature-dependent electronic structure has been observed for this salt. Here, DFT calculations performed on 3 confirm the previous assignments of spin- and oxidation-states. Thus, [Fe(pda)(2)](n) (n=0, 1-, 2-) constitutes an electron-transfer series, which has also been established by cyclic voltammetry; the mono- and dications (n=1+ and 2+) are also accessible in solution, but have not been further investigated. The (57)Fe Mössbauer spectra of [Fe(pda)(2)](n) species in 1 and 3 show extremely large quadrupole splitting constants due to addition of the valence and covalence contributions that have been confirmed by DFT calculations.