Fernande Grandjean

Selective Binding of O2 over N2 in a Redox–Active Metal–Organic Framework with Open Iron(II) Coordination Sites

The air-free reaction between FeCl(2) and H(4)dobdc (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe(2)(dobdc)·4DMF, a metal-organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer-Emmett-Teller (BET) surface area of 1360 m(2)/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe(II) centers. Gas adsorption isotherms at 298 K indicate that Fe(2)(dobdc) binds O(2) preferentially over N(2), with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O(2) molecule per two iron centers. Remarkably, at 211 K, O(2) uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O(2) molecule per iron center. Mössbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O(2) at low temperature and complete charge transfer to form iron(III) and O(2)(2-) at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O(2) bound to iron in a symmetric side-on mode with d(O-O) = 1.25(1) Å at low temperature and in a slipped side-on mode with d(O-O) = 1.6(1) Å when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe(2)(dobdc) to be a promising material for the separation of O(2) from air at temperatures well above those currently employed in industrial settings.

Slow Magnetic Relaxation in a Family of Trigonal Pyramidal Iron(II) Pyrrolide Complexes

We present a family of trigonal pyramidal iron(II) complexes supported by tris(pyrrolyl-α-methyl)amine ligands of the general formula [M(solv)(n)][(tpa(R))Fe] (M = Na, R = tert-butyl (1), phenyl (4); M = K, R = mesityl (2), 2,4,6-triisopropylphenyl (3), 2,6-difluorophenyl (5)) and their characterization by X-ray crystallography, Mössbauer spectroscopy, and high-field EPR spectroscopy. Expanding on the discovery of slow magnetic relaxation in the recently reported mesityl derivative 2, this homologous series of high-spin iron(II) complexes enables an initial probe of how the ligand field influences the static and dynamic magnetic behavior. Magnetization experiments reveal large, uniaxial zero-field splitting parameters of D = -48, -44, -30, -26, and -6.2 cm(-1) for 1-5, respectively, demonstrating that the strength of axial magnetic anisotropy scales with increasing ligand field strength at the iron(II) center. In the case of 2,6-difluorophenyl substituted 5, high-field EPR experiments provide an independent determination of the zero-field splitting parameter (D = -4.397(9) cm(-1)) that is in reasonable agreement with that obtained from fits to magnetization data. Ac magnetic susceptibility measurements indicate field-dependent, thermally activated spin reversal barriers in complexes 1, 2, and 4 of U(eff) = 65, 42, and 25 cm(-1), respectively, with the barrier of 1 constituting the highest relaxation barrier yet observed for a mononuclear transition metal complex. In addition, in the case of 1, the large range of temperatures in which slow relaxation is observed has enabled us to fit the entire Arrhenius curve simultaneously to three distinct relaxation processes. Finally, zero-field Mössbauer spectra collected for 1 and 4 also reveal the presence of slow magnetic relaxation, with two independent relaxation barriers in 4 corresponding to the barrier obtained from ac susceptibility data and to the 3D energy gap between the M(S) = ±2 and ±1 levels, respectively.

Some physical properties of LaFe4P12 type compounds

Abstract Several pnictides with the filled skutterudite (LaFe 4 P 12 type) structure were investigated by X-ray diffraction, magnetic susceptibility and electrical conductivity measurements and Mossbauer spectroscopy. The structure refinement of CeFe 4 P 12 from single crystal X-ray data resulted in a conventional residual value of 0.022 for 11 variable parameters and 317 reflections. LaFe 4 P 12 and CeFe 4 P 12 are paramagnetic at room temperature. EuFe 4 P 12 is a ferromagnet with a Curie temperature of 99 K. CeFe 4 P 12 and CeFe 4 As 12 are semiconducting. LaFe 4 Pn 12 ( Pn = P , As or Sb ) and CeFe 4 Sb 12 show metallic conductivity. The room temperature 57 Fe Mossbauer spectra of LaFe 4 P 12 , CeFe 4 P 12 and EuFe 4 P 12 are symmetrical doublets. The isomer shifts are compatible with low spin or metallic Fe. At 1.5 K the 57 Fe Mossbauer spectrum of EuFe 4 P 12 under an external field shows that Fe does not carry any magnetic moment. 151 Eu Mossbauer spectra of EuFe 4 P 12 at 4.2 and 300 K show unusual hyperfine parameters.

57Fe hyperfine interaction parameters and selected magnetic properties of high purity MFe12O19 (M=Sr, Ba)

Much of the confusion regarding the 57Fe Mossbauer spectroscopic hyperfine parameters of SrFe12O19 and BaFe12O19 at 300 K has been removed by means of an interlaboratory investigation of well-characterized samples prepared from high purity starting materials. In contrast to previous investigations, the contributions of each of the five Fe sublattices to the Mossbauer spectrum are discernible at 300 K and five components are necessary for an adequate fit of the data. The relative magnitudes of the hyperfine fields, Hn, and isomer shifts, δ, are as follows: for SrFe12O19 and BaFe12O19: Hn(2b)< Hn(12k)<Hn(4f1) <Hn(2a)<Hn(4f2), for SrFe12O19 δ(4f1≤δ(2b)<δ(12k)δ(2a)<δ(4f2), and for BaFe12O19 δ4f2), and for BaFe12O19 δ(4f1<δ(4f1)<(12k) < δ(4f2)<δ(2a). The above assignment is based on considerations of both magnetic and crystal/chemical structures. The high purity starting materials seem to have appreciable influences on both hyperfine interaction parameters and bulk magnetic properties as observed by others for spinel and garnet ferrites.

A neutron diffraction and Mössbauer effect study of the Nd2Fe17−xSix solid solutions

Abstract The substitution of silicon for iron in Nd 2 Fe 17 strongly raises the Curie temperature but leads to a reduction in the unit cell volume. Refinement of the neutron-diffraction pattern for Nd 2 Fe 12.91 Si 4.09 indicates that silicon preferentially occupies the 18h site in the Nd 2 Fe 17 structure, the site with the most neodymium near neighbors. This occupation is surprising because conventional arguments would suggest that replacement of iron on the 6c site, which has a very short iron to near-neighbor iron bond length, would yield an increase in the Curie temperature.

A Mössbauer effect study of the microscopic magnetic properties of Nd2Fe17 and Nd2Fe17N2.6

The Mossbauer spectra of Nd2Fe17 and Nd2Fe17N2.6 have been measured at various temperatures between 78 and 295 K and analyzed with a model that is based on the Wigner–Seitz cell environment of each iron site, the orientation of the magnetization, and the magnetic moments as determined from either neutron‐diffraction measurements or band‐structure calculations. Upon nitrogenation of Nd2Fe17, the weighted average isomer shift increases from 0.060 to 0.164 mm/s and further the isomer shifts of the four crystallographically distinct sites increase in agreement with the increase observed in their Wigner–Seitz cell volumes and the presence of a nitrogen near neighbor for two of the sites. Upon nitrogenation of Nd2Fe17, the weighted average hyperfine field increases from 292.3 to 333.8 kOe. However, the increases on the 6c and 18f sites are much smaller than those observed on the 9d and 18h sites; changes which are in agreement with calculated changes in the magnetic moments upon nitrogenation of Nd2Fe17, Gd2Fe1...

Neutron diffraction and Mössbauer effect study of several Nd2Fe17−xAlx solid solutions

Aluminum‐substituted Nd2Fe17−xAlx solid solutions with x=2.30, 4.44, 6.13, 8.00, and 9.40 have been studied by neutron diffraction and Mossbauer spectroscopy. A Rietveld analysis of the neutron scattering indicates that the aluminum atoms have a high initial affinity for the 18h site, show a high affinity for the 6c site at high aluminum concentrations, and are absent from the 9d site at all aluminum concentrations. The Mossbauer spectra show a maximum in both the maximum and weighted average hyperfine field for x≊2. This indicates that the lattice expansion which occurs with aluminum substitution is sufficient, at least for small values of x, where magnetic dilution is small, to enhance the intrasublattice coupling between the iron moments, and to increase the magnetic hyperfine fields.

Mössbauer spectroscopy as a probe of magnetization dynamics in the linear iron(I) and iron(II) complexes [Fe(C(SiMe3)3)2](1-/0.).

The iron-57 Mössbauer spectra of the linear, two-coordinate complexes, [K(crypt-222)][Fe(C(SiMe3)3)2], 1, and Fe(C(SiMe3)3)2, 2, were measured between 5 and 295 K under zero applied direct current (dc) field. These spectra were analyzed with a relaxation profile that models the relaxation of the hyperfine field associated with the inversion of the iron cation spin. Because of the lifetime of the measurement (10(-8) to 10(-9) s), iron-57 Mössbauer spectroscopy yielded the magnetization dynamics of 1 and 2 on a significantly faster time scale than was previously possible with alternating current (ac) magnetometry. From the modeling of the Mössbauer spectral profiles, Arrhenius plots between 5 and 295 K were obtained for both 1 and 2. The high-temperature regimes revealed Orbach relaxation processes with U(eff) = 246(3) and 178(9) cm(-1) for 1 and 2, respectively, effective relaxation barriers which are in agreement with magnetic measurements and supporting ab initio calculations. In 1, two distinct high-temperature regimes of magnetic relaxation are observed with mechanisms that correspond to two distinct single-excitation Orbach processes within the ground-state spin-orbit coupled manifold of the iron(I) ion. For 2, Mössbauer spectroscopy yields the temperature dependence of the magnetic relaxation in zero applied dc field, a relaxation that could not be observed with zero-field ac magnetometry. The ab initio calculated Mössbauer hyperfine parameters of both 1 and 2 are in excellent agreement with the observed hyperfine parameters.

Dispersion Force Stabilized Two-Coordinate Transition Metal???Amido Complexes of the ???N({SiMe}

A series of high spin, two-coordinate first row transition metal-amido complexes, M{N(SiMe3)Dipp}2 {M = Fe (1), Co (2), or Ni (3); Dipp = C6H3-2,6-Pr(i)2} and a tetranuclear C-H activated chromium amide, [Cr{N(SiMe2CH2)Dipp}2Cr]2(THF) (4), were synthesized by reaction of their respective metal dihalides with 2 equiv of the lithium amide salt. They were characterized by X-ray crystallography, electronic and infrared spectroscopy, SQUID magnetic measurements, and computational methods. Contrary to steric considerations, the structures of 1-3 display planar eclipsed M{NSiC(ipso)}2 arrays and short M-N distances. DFT calculations, corrected for dispersion effects, show that dispersion interactions involving C-H-H-C moieties likely stabilize the structures by 21.1-29.4 kcal mol(-1), depending on the level of the calculations employed. SQUID measurements confirm high spin electron configurations for all the complexes and substantial orbital contributions for 1 and 2.

_{\textrm{3}}

A three-dimensional mixed-valent iron(II,III) trans-1,4-cyclohexanedicarboxylate, 1,4-chdc, coordination polymer, [Fe(II)Fe(III)(mu(4)-O)(1,4-chdc)(1.5)](infinity), 1, has been synthesized hydrothermally by mixing iron powder and 1,4-chdcH(2) and investigated by X-ray diffraction, dc and ac magnetic susceptibility, and iron-57 Mossbauer spectroscopy over a wide range of temperatures. Single-crystal X-ray diffraction studies of 1 at 90(2), 293(2), and 473(2) K reveal a tetrahedral [Fe(II)(2)(mu(4)-O)Fe(III)(2)(mu(4)-O)](6+) mixed-spin-chain structure with no change in the P1 space group but with subtle changes in the Fe-O and Fe...Fe distances with increasing temperature. These changes are associated with the electron delocalization observed by Mossbauer spectroscopy above 225 K. Magnetic studies reveal three different magnetic regimes in 1 between 2 and 320 K. Above 36 K 1 is a one-dimensional ferrimagnetic-like complex with frustration arising from competing exchange interactions between the iron(II) and iron(III) ions in the chains. Between 36 and 25 K the interchain interactions are non-negligible and 1 undergoes three-dimensional ordering at 32.16 K but with some residual fluctuations. Below 25 K the residual fluctuations slow and eventually freeze below 15 K; the small net moment of 0.22 mu(B) per mole of 1 observed below 15 K may be attributed to a non-collinear or canted spin structure of the spins of the four iron ions in the [Fe(II)(2)(mu(4)-O)Fe(III)(2)(mu(4)-O)](6+) chains. Below 32 K the Mossbauer spectra of 1 exhibit sharp sextets for both the iron(III) and iron(II) ions and are consistent with either a static long-range or a short-range magnetic ground state or a slow relaxation between two canted magnetic states that are indistinguishable at the observed spectral resolution. The 85 and 155 K spectra reveal no electron delocalization and correspond solely to fixed valence iron(II) and iron(III). Between 225 and 310 K the spectra reveal the onset of electron delocalization such that, at 295 to 310 K, 25, 25, and 50% of the iron in 1 is present as iron(II), iron(III), and iron(II/III) ions, respectively. The absence of any spectral line broadening associated with this electron delocalization and the coexistence of four doublets between 225 and 310 K indicate that the delocalization occurs through electron tunneling via vibronic coupling. The sudden increase in the tunneling rate beginning above about 260 K and the presence of a cusp in the magnetic susceptibility centered at about 275 K strongly suggest the existence of a charge order/disorder transition whose nature and order are discussed.