Slow magnetic relaxation and electron delocalization in an S = 9/2 iron(II∕III) complex with two crystallographically inequivalent iron sites

The magnetic, electronic, and Mo?ssbauer spectral properties of [Fe(2)L(μ-OAc)(2)]ClO(4), 1, where L is the dianion of the tetraimino-diphenolate macrocyclic ligand, H(2)L, indicate that 1 is a class III mixed valence iron(II∕III) complex with an electron that is fully delocalized between two crystallographically inequivalent iron sites to yield a [Fe(2)](V) cationic configuration with a S(t) = 9∕2 ground state. Fits of the dc magnetic susceptibility between 2 and 300 K and of the isofield variable-temperature magnetization of 1 yield an isotropic magnetic exchange parameter, J, of -32(2) cm(-1) for an electron transfer parameter, B, of 950 cm(-1), a zero-field uniaxial D(9∕2) parameter of -0.9(1) cm(-1), and g = 1.95(5). In agreement with the presence of uniaxial magnetic anisotropy, ac susceptibility measurements reveal that 1 is a single-molecule magnet at low temperature with a single molecule magnetic effective relaxation barrier, U(eff), of 9.8 cm(-1). At 5.25 K the Mo?ssbauer spectra of 1 exhibit two spectral components, assigned to the two crystallographically inequivalent iron sites with a static effective hyperfine field; as the temperature increases from 7 to 310 K, the spectra exhibit increasingly rapid relaxation of the hyperfine field on the iron-57 Larmor precession time of 5 × 10(-8) s. A fit of the temperature dependence of the average effective hyperfine field yields |D(9∕2)| = 0.9 cm(-1). An Arrhenius plot of the logarithm of the relaxation frequency between 5 and 85 K yields a relaxation barrier of 17 cm(-1).     

Poly[(2,2'-bipyridine)tetrakis(imidazolato)diiron(II)]: structural and spin-state phase transitions and low-temperature magnetic ordering in a unique 2-dimensional material

Poly[(2,2'-bipyridine)tetrakis(imidazolato)diiron(II)] was synthesized by the reaction of ferrocene with imidazole in an excess of 2,2'- bipyridine in a Carius tube at 130 degrees C. Dc magnetic susceptibility studies at an applied field of 1000 G reveal that on cooling from room temperature, the material undergoes two structural phase transitions designated alpha --> beta and beta --> gamma at 151 and 133 K, respectively. On warming, the gamma --> beta and beta --> alpha transitions are observed at 137 and 151 K, respectively; a 4 K thermal hysteresis clearly detectable in the lower temperature beta <--> gamma transition. These structural phase transitions have also been studied by detailed, variable-temperature, ac susceptibility and M?ssbauer spectroscopy techniques. Single-crystal X-ray diffraction studies done at 294, 143, and 113 K reveal 2, 12, and 6 unique iron centers in the alpha-, beta-, and gamma-forms, respectively. All three forms have the same basic structure involving 2D extended double layer sheets (bilayers) of alternating tetrahedral and octahedral irons singly bridged by imidazolate ligands, with the octahedral centers additionally coordinated by 2,2'-bipyridine ligands that occupy positions between the sheets. Magnetic susceptibility and bond length data reveal that in the gamma-phase one in three six-coordinate sites corresponds to spin singlet ground-state iron(II); i.e., the overall alpha --> gamma process involves a spin-crossover transition such that at least 1/6 of the iron sites in the gamma-phase correspond to S = 0. This is supported by the low-temperature M?ssbauer spectra of the gamma-phase, which reveal the simultaneous presence of both S = 2 and S = 0 iron(II) centers. The compound magnetically orders, with a resultant small remnant magnetization, at low temperatures. The magnetic phase transition, studied by a combination of dc and ac susceptibility and M?ssbauer techniques, occurs at T(c) approximately 6.5 K.     

Structural and physical properties of the ferromagnetic tris-dithiooxalato compounds,A[M(II)Cr(III)(C(2)S(2)O(2))(3)], with A(+) = N(n-C(n)()H(2)(n)(+1))(4)(+) (n = 3-5) and P(C(6)H(5))(4)(+) and M(II) = Mn,Fe, Co,and Ni

The structural and magnetic properties of the tris-dithiooxalato salts, A[M(II)Cr(C(2)S(2)O(2))(3)], have been investigated with A(+) = PPh(4)(+), N(n-C(n)()H(2)(n)()(+1))(4)(+), with n = 3-5, where M(II) is Mn, Fe, Co, and Ni. With the exception of A[MnCr(C(2)S(2)O(2))(3)], all the salts are ferromagnets with Curie temperatures, T(c), between 5 and 16 K. In contrast to the corresponding oxalates which are ferromagnetic, the A[MnCr(C(2)S(2)O(2))(3)] compounds are paramagnetic above 2 K. Powder neutron diffraction studies of d(20)-PPh(4)[FeCr(C(2)S(2)O(2))(3)] indicate that no structural phase transitions occur between 2.4 and 285 K and that the coefficient of linear expansion is four times larger for the c-axis than for the a-axis. The crystal structure refined from powder neutron diffraction data confirms the honeycomb layer arrangement observed in the related bimetallic tris-oxalate salts. The M?ssbauer spectra reveal that the iron(II) in PPh(4)[FeCr(C(2)S(2)O(2))(3)] is coordinated mainly to six oxygen atoms of the dithiooxalato ligand but with a minor component of sulfur coordination that increases with aging of the sample; the iron(II) is high-spin in both cases. Powder neutron diffraction profiles of d(20)-PPh(4)[FeCr(C(2)S(2)O(2))(3)] below T(c) show magnetic intensity with a q = 0 propagation vector, confirming the presence of ferromagnetic order.     

Spin crossover in a tetranuclear Cr(III)-Fe(III)(3) complex

A novel heteronuclear exchange-coupled complex [Cr(III)[(CN)Fe(III)((5)L)](3)(CN)(3)] containing a pentadentate blocking ligand (5)L was synthesized. The X-ray structure shows that a meridional isomer applies with inequivalent Fe(III) centers. The complex exhibits a thermally induced spin crossover along with the exchange coupling. M?ssbauer spectra indicate a spin transition between S = (1)/(2) and S = (5)/(2) states although a considerable amount of Fe(III) centers stays high-spin at T = 6 K. The magnetization, the magnetic susceptibility, and the M?ssbauer data were fitted in one run with a spin crossover model taking into account exchange interactions among all metal centers.     

Synthesis and spectral characterization of some oxo-centered,trinuclear mixed-valence iron thiocarboxylates

Some mixed-valence Fe(II) Fe(III) complexes of thiocarboxylic acids and straight chain fatty acids with general formula [Fe(II)Fe(III)(2)O(SOCR)(6)(H(2)O)(3)] and [Fe(II)Fe(III)(2)O(SOCR)(3)(OOCR')(3)(CH(3)OH)(3)] (where, R=CH(3) or C(6)H(5) and R'=C(13)H(27), C(15)H(31) or C(17)H(35)) were synthesized and characterized by elemental analyses, spectral (infrared, electronic and M?ssbauer) studies, molar conductance and magnetic susceptibility measurements. The infrared spectra suggested bridging nature of carboxylate and thiocarboxylate anions along with upsilon(asym)(Fe(3)O) vibrations in the complexes. M?ssbauer studies revealed two resolved quadrupole doublets at 120-315 K confirming the presence of Fe(II) and Fe(III) moieties in the complexes. This was supported by the observed electronic spectral bands in the complexes at room temperature. The spectrum showed a band at around 13,800 cm(-1) which indicated an intervalence-transfer. Magnetic susceptibility measurements showed weak antiferromagnetic coupling related to mixed-valence pairs with S(2)=2, em leader S(1)=S(3)=5/2 spin exchange model. Conductance data indicated, the complexes were non-electrolytes in nitrobenzene. A structure has been established on the basis of these studies.     

Characterization of iron promoter in tungstated zirconia catalysts by Mössbauer spectroscopy at very low temperatures

A tungstated zirconia (WZ) catalyst with iron promoter used for the conversion of n-pentane into isopentane has been characterized by M?ssbauer spectroscopy. The M?ssbauer spectra have been recorded in zero magnetic field in the temperature range 0.05-295 K and with a magnetic field up to 7 T between 4.2 and 50 K. Both the recording of M?ssbauer spectra with an applied magnetic field and at extremely low temperature allowed for the demonstration that iron is present in the catalysts as (i) hematite (alpha-Fe2O3) particles a few 10 nm in size, (ii) very small oligomeric Fe(III) species, probably in solid solution in zirconia, and (iii) Fe(III) oxide clusters showing magnetic ordering, probably embedded in the first surface layer and thus forming "rafts". These latter clusters form two ensembles with quite different sizes: one with diameters of about 3 nm, the other with diameters larger than 30 nm. These results are in agreement with those recently obtained by X-ray absorption spectroscopy and electron paramagnetic resonance.     

A two-dimensional iron(II) carboxylate linear chain polymer that exhibits a metamagnetic spin-canted antiferromagnetic to single-chain magnetic transition

A two-dimensional iron(II) carboxylate coordination polymer, [Fe(pyoa)2]infinity, where pyoa is 2-(pyridin-3-yloxy)acetate, has been prepared by hydrothermal synthesis. Its crystal structure reveals a single iron(II) site with an elongated octahedral coordination environment containing four equatorial carboxylate oxygens and two axial pyridyl nitrogens; the iron(II) sites are linked by syn-anti micro-carboxylates to form chains along the b axis that have an Fe...Fe separation of 4.910 A. The shortest interchain and interlayer Fe...Fe distances are 6.453 and 11.125 A, respectively. The 4.2-295 K M?ssbauer spectra of [Fe(pyoa) 2] infinity consist of a single paramagnetic high-spin iron(II) quadrupole doublet. The axial Fe-N bond direction defines the Jahn-Teller axis at an iron(II) site and, consequently, the orientation of the single-ion magnetic anisotropy. Thus, along the b axis in a given chain, the spins are collinear and parallel to the Jahn-Teller axis. The Jahn-Teller axes of adjacent intralayer chains have different orientations with an angle of 79.2 degrees between the axes in adjacent chains in a bc layer. [Fe(pyoa)2]infinity exhibits field-induced metamagnetic behavior such that, in an applied field smaller than the critical field, the iron(II) spin-canted moments experience intrachain ferromagnetic interactions and weak interchain antiferromagnetic interactions; the spin canting yields weak ferromagnetism. In an applied field larger than the critical field, the weak antiferromagnetic interchain interactions are overwhelmed to yield superparamagnetic-like slow-magnetic relaxation with an energy barrier of 23(3) K. Single-crystal magnetic studies reveal a quasi-uniaxial magnetic anisotropy with the a axis as the easy-magnetic axis and the b axis as the hard-magnetic axis; the susceptibility measured along the easy a axis may be fit with the Glauber model to yield an effective intrachain exchange coupling constant of 2.06(8) K. A dynamic analysis of the susceptibility yields a 6.3(1) K energy barrier for intrachain domain wall creation. The observed field-assisted superparamagnet-like behavior is consistent with the dynamics of a single-chain magnet. Thus, [Fe(pyoa)2]infinity is best considered as a "metamagnetic-like" single-chain magnet.     

Mononuclear (nitrido)iron(V) and (oxo)iron(IV) complexes via photolysis of [(cyclam-acetato)FeIII(N3)]+ and ozonolysis of [(cyclam-acetato)FeIII(O3SCF3)]+ in water/acetone mixtures

Reaction of the monoanionic, pentacoordinate ligand lithium 1,4,8,11-tetraazacyclotetradecane-1-acetate, Li(cyclam-acetate), with FeCl3 yields, upon addition of KPF6, [(cyclam-acetato)FeCl]PF6 (1) as a red microcrystalline solid. Addition of excess NaN3 prior to addition of KPF6 yields the azide derivative [(cyclam-acetato)FeN3]PF6 (2a) as orange microcrystals. The X-ray crystal structure of the azide derivative has been determined as the tetraphenylborate salt (2b). Reaction of 1 with silver triflate yields [(cyclam-acetato)Fe(O3SCF3)]PF6 (3), which partially dissociates triflate in nondried solvents to yield a mixture of triflate and aqua bound species. Each of the iron(III) derivatives is low-spin (d5, S = 1/2) as determined by variable-temperature magnetic susceptibility measurements, M?ssbauer and EPR spectroscopy. The low-spin iron(II) (d6, S = 0) complexes 1red and 2ared have been prepared by electrochemical and chemical methods and have been characterized by M?ssbauer spectroscopy. Photolysis of 2a at 419 nm in frozen acetonitrile yields a nearly colorless species in approximately 80% conversion with an isomer shift delta = -0.04 mm/s and a quadrupole splitting delta EQ = -1.67 mm/s. A spin-Hamiltonian analysis of the magnetic M?ssbauer spectra is consistent with an FeV ion (d3, S = 3/2). The proposed [(cyclam-acetato)FeV=N]+ results from the photooxidation of 2a via heterolytic N-N cleavage of coordinated azide. Photolysis of 2a in acetonitrile solution at -35 degrees C (300 nm) or 20 degrees C (Hg immersion lamp) results primarily in photoreduction via homolytic Fe-Nazide cleavage yielding FeII (d,6 S = 0) with an isomer shift delta = 0.56 mm/s and quadrupole splitting delta EQ = 0.54 mm/s. A minor product containing high-valent iron is suggested by M?ssbauer spectroscopy and is proposed to originate from [((cyclam-acetato)Fe)2(mu-N)]2+ with a mixed-valent (FeIV(mu-N)FeIII))4+S = 1/2 core. Exposure of 3 to a stream of oxygen/ozone at low temperatures (-80 degrees C) in acetone/water results in a single oxidized product with an isomer shift delta = 0.01 mm/s and quadrupole splitting delta EQ = 1.37 mm/s. A spin-Hamiltonian analysis of the magnetic M?ssbauer yields parameters similar to those of compound II of horseradish peroxidase which are consistent with an FeIV=O monomeric complex (S = 1).     

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.     

A study of the new cubic,ordered perovskites BaLaMRuO6 (M = Mg,Fe, Co,Ni, or Zn) and the related phases La2MRuO6 (M = Mg,Co, Ni,or Zn) by 99Ru Mössbauer spectroscopy and other techniques

⁵⁷Fe and ⁹⁹Ru Mössbauer spectroscopy, coupled with magnetic susceptibility measurements down to 4.2 K, have been used to study the electronic and magnetic properties of the new cubic-ordered perovskites BaLaMRuO₆ (M = Mg, Fe, Co, Ni, or Zn). The ruthenium is present in the +5 oxidation state in all the compounds except BaLaFeRuO₆ which contains iron(III) and ruthenium(IV). All the compounds exhibit long-range antiferromagnetic order, with Néel temperatures in the range 20–40 K. Mössbauer spectra for the new compound La₂CoRuO₆ and the isostructural cubic perovskites La₂MRuO₆ (M = Mg, Ni, or Zn) confirm the presence of ruthenium(IV) in these phases and indicate that they are not ordered magnetically at 4.2 K.     

First dicyanamide-bridged spin-crossover coordination polymer: synthesis, structural, magnetic, and spectroscopic studies

We report here on the synthesis and characterisation of a first iron(II) spin-crossover coordination polymer with the dca spacer ligand, having the formula [Fe(aqin)2(dca)]ClO4.MeOH (aqin=8-aminoquinoline, dca=dicyanamide), which displays a two-step complete spin transition. Variable-temperature magnetic susceptibility measurements and M?ssbauer spectroscopy have revealed that the two relatively gradual steps are centred at 215 and 186 K and are separated by an inflection point at about 201 K, at which 50 % of the complex molecules undergo a spin transition. The two steps are related to the existence of two crystallographically inequivalent metal sites, as confirmed by the structural and M?ssbauer studies. The crystal structure was resolved at 293 K (HS form) and 130 K (LS form). Both spin-state structures belong to the triclinic P1 space group (Z=2). The complex assumes a linear chain structure, in which the active iron(II) sites are linked to each other by anionic dicyanamide ligands acting as chemical bridges. The Fe-Fe distances through the dca ligand are 8.119(1) and 7.835(1) A in the high-spin and low-spin structures, respectively. The polymeric chains extend along a (1, 0, -1) axis and are packed in sheets, between which the perchlorate anions and methanol molecules are inserted. The complex molecules are linked together by pi-stacking interactions and H-bonding between the H-donor aqin ligands and the perchlorate ions. These structural features provide a basis for cooperative interactions in the crystal lattice. Analysis of the two-step spin-crossover character in this compound suggests that covalent interactions through the spacer ligand do not provide the main mechanism of cooperativity.     

Electronic, magnetic, and structural characterization of the five-coordinate, high-spin iron(II) nitrato complex [Fe(TpivPP)(NO3)]-

The preparation and characterization of the five-coordinate iron(II) porphyrinate derivative [Fe(TpivPP)(NO3)]- (TpivPP = picket-fence porphyrin) is described. Structural and magnetic susceptibility data support a high-spin state (S = 2) assignment for this species. The anionic axial nitrate ligand is O-bound, through a single O atom, with an Fe-O bond length of 2.069(4) A. The planar nitrate ligand bisects a N(p)-Fe-N(p) angle. The average Fe-N(p) bond length is 2.070(16) A. The Fe atom is located 0.49 A out of the 24-atom mean porphyrin plane toward the nitrate ligand. From solid-state M?ssbauer data, the isomer shift of 0.98 mm/s at 77 K is entirely consistent with high-spin iron(II). However the quadrupole splitting of 3.59 mm/s at 77 K is unusually high for iron(II), S = 2 systems but within the range of other five-coordinate high-spin ferrous complexes with a single anionic axial ligand. Crystal data for [K(222)][Fe(TpivPP)(NO3)] x C6H5Cl: a = 17.888 (5) A, b = 21.500 (10) A, c = 22.514 (11) A, beta = 100.32 (3) degrees, monoclinic, space group P2(1)/n, V = 8519 A3, Z = 4.     

Crystal structure and magnetic properties of tris(2-hydroxymethyl-4-oxo-4H-pyran- 5-olato-κ2O5,O4)iron(III)

Tris(2-hydroxymethyl-4-oxo-4H-pyran-5-olato-κ²O⁵,O⁴)iron(III) [Fe(ka)₃], has been characterised by magnetic susceptibility measurements Mössbauer and EPR spectroscopy. The crystal structure of [Fe(ka)₃] has been determined by powder X-ray diffraction analysis. Magnetic susceptibility and EPR measurements indicated a paramagnetic high-spin iron centre. Mössbauer spectra revealed the presence of magnetic hyperfine interactions that are temperature-independent down to 4.2?K. The interionic Fe³⁺ distance of 7.31?Å suggests spin-spin relaxation as the origin of these interactions.     

Effects of the host matrix on the 57Fe-species produced through EC-decay in 57Co-labelled tris(phenanthroline) cobalt (II) perchlorate.

Emission M?ssbauer spectroscopic studies of 57Co-labelled [Co(phen)3]clO4)2 in host matrices [M(II)(phen)3](ClO4)2(M=Co, Fe, and Ni) indicate that the relative intensities of the anomalous species produced through the EC-decay depend on the kind of the host matrix. The largest intensity was observed with the cobalt (II) matrix, and the smallest with the iron (II) matrix. Emission spectra of 57Co-labelled [Co(2-CH3-phen)3](ClO4)2 2H2O in the matrix of [Fe(2-CH3-phen)3](ClO4)2 were also studied. The high-spin state (5T2) was predominantly observed at 4.2 K in the emission spectrum, while the low-spin state (1A1) was mainly observed in the absorption spectrum at 78 K. The results are discussed in terms of the stability of the lattice.     

K4Fe4P5O20: a new mixed valence microporous compound with elliptical eight-ring channels

A new small-pore compound K(4)Fe(4)P(5)O(20) was obtained by conventional solid-state reaction in a closed crucible. The crystal structure is constructed by Fe(4)P(5)O(20) units forming chains along the c axis and elliptical eight-ring channels on the a-b plane in which K cations locate inside. Such structural characteristics seem to be quite similar to those seen in the natrolite family. However, Fe ions in K(4)Fe(4)P(5)O(20) have trigonal-bipyramidal instead of common tetrahedral coordination. Furthermore, our experimental results combined from magnetic susceptibility and (57)Fe M?ssbauer spectrum measurements show mixed valence Fe(3+)/Fe(2+) in the titled material. To the best of our knowledge, this is the first example that contains mixed valence iron ions in a so-called natrolite framework.     

Iron complexes of new pentadentate ligands containing the 1,4,7-triazacyclononane-1,4-diacetate motif. spectroscopic, electro-, and photochemical studies

Three new pentadentate, pendent arm macrocycles containing the 1,4,7-triazacyclononane-1,4-diacetate motif have been synthesized, and their coordination chemistry with Fe(III) has been investigated. Eight new octahedral Fe(III) complexes containing chloro, azido, or mu-oxo ligands have been synthesized, five of which have been characterized by X-ray crystallography. Spectroscopic characterization of these octahedral Fe(III) complexes by UV-vis, IR, electrochemistry, EPR, magnetic susceptibility, and zero-field M?ssbauer measurements firmly establishes the high-spin state of the iron in all complexes. Electrochemistry studies of the azido-Fe(III) complexes show that they can be reversibly oxidized to the corresponding Fe(IV) species at -20 degrees C, and Fe(II), Fe(III), and Fe(IV) species show characteristic IR and UV-vis profiles. Photolysis of one of the azido complexes was studied as a function of temperature (room temperature vs 77 K) and wavelength (480, 419, and 330 nm). Photoreduction to a high-spin Fe(II) species occurs under all conditions, which is proposed to be the dominant photochemical pathway generally available to high-spin ferric azido complexes.     

Mössbauer studies of the iron-sulfur cluster-free hydrogenase: the electronic state of the mononuclear Fe active site

The iron-sulfur cluster-free hydrogenase (Hmd) from methanogenic archaea harbors an iron-containing, light-sensitive cofactor of still unknown structure as prosthetic group. The enzyme is reversibly inhibited by CO and cyanide and is EPR silent. We report here on M?ssbauer spectra of the (57)Fe-labeled enzyme and of the isolated cofactor. The spectrum of the holoenzyme measured at 80 K revealed a doublet peak with an isomer shift delta = 0.06 mm.s(-)(1) and a quadrupole splitting of DeltaE(Q) = 0.65 mm.s(-)(1) (at pH 8.0). The signal intensity corresponded to the enzyme concentration assuming 1 Fe per mol active site. Upon addition of CO or cyanide to the enzyme, the isomer shift decreased to -0.03 mm.s(-)(1) and -0.00(1) mm.s(-)(1), and the quadrupole splitting increased to 1.38 mm.s(-)(1) and 1.75 mm.s(-)(1), respectively. The three spectra could be perfectly simulated assuming the presence of only one type of iron in Hmd. The low isomer shift is characteristic for Fe in a low oxidation state (0, +1, +2). When the spectra of the holoenzyme and of the CO- or cyanide-inhibited enzyme were measured at 4 K in a magnetic field of 4 and 7 T, the spectra obtained could be simulated assuming the presence of only the external magnetic field, which excludes that the iron in the active site of Hmd is Fe(I), high-spin Fe(0), or high-spin Fe(II). M?ssbauer spectra of the isolated Hmd cofactor are also reported.     

Thermal and Light-Induced Spin Transition in the High- and Low-Temperature Structure of [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2)

The thermal and light induced spin transition in [Fe(0.35)Ni(0.65)(mtz)(6)](ClO(4))(2) (mtz = 1-methyl-1H-tetrazole) was studied by (57)Fe M?ssbauer spectroscopy and magnetic susceptibility measurements. In addition to the spin transition of the iron(II) complexes the compound undergoes a structural phase transition. The high-temperature structure could be determined by X-ray crystallography of the isomorphous [Fe(0.25)Ni(0.75)(mtz)(6)](ClO(4))(2) complex at room temperature. The X-ray structural analysis shows this complex to be rhombohedric, space group R&thremacr;, with a = 10.865(2) ? and c = 23.65(1) ? with three molecules in the unit cell. The transition to the low-temperature structure occurs at approximately 60 K without changing the spin state of the molecules. By subsequent heating of the complex the high-temperature structure is reached again between ca. 170 and 200 K. The spin transition behavior is strongly influenced by the structural changes, and the observed spin transition curves are completely different for the high- and low-temperature phases. In the high-temperature structure a complete and gradual spin transition between 220 and 120 K (T(1/2)(gamma(HS) = 0.5) = 185 K) is detected; the high-spin (HS) state is represented by one HS doublet in the M?ssbauer spectra. In the low-temperature structure a two-step transition curve is detected in the heating mode. About 36% of the molecules show a LS (low-spin) --> HS transition between ca 50 and 75 K. Then the HS fraction stays constant up to 150 K. A further increase in the high-spin fraction is observed at temperatures above 150 K. In this structural phase the HS state is represented by two different HS doublets in the M?ssbauer spectra. The formation of metastable HS states by making use of the LIESST effect is only possible in the low-temperature structure. By excitation of the LS molecules with green light, two different HS states are populated which show very different relaxation behavior. One HS state shows a relaxation to the LS state even at 10 K; the other HS state shows a very slow HS --> LS relaxation at 60 K (within days), leading to the HS fraction corresponding to the thermal equilibrium value.     

Parametrization of the magnetic behavior of the triangular spin ladder chains organically templated: (C2N2H10)[M(HPO3)F3] (M(III) = Fe, Cr, and V). Crystal structure and thermal and spectroscopic properties of the iron(III) phase

A new iron(III) phosphite templated by ethylenediamine has been synthesized using solvothermal conditions under autogenous pressure. The (C2N2H10)[Fe(HPO3)F3] compound has been characterized by single-crystal X-ray diffraction data and spectroscopic and magnetic techniques. The crystal structure is formed by chains extended along the c axis and surrounded by ethylenediammonium cations. A study by diffuse-reflectance spectroscopy has been performed, and the calculated Dq, B, and C parameters for the Fe(III) cations are 1030, 720, and 3080 cm(-1), respectively. The M?ssbauer spectrum at room temperature is characteristic of Fe(III) ions. The electron spin resonance (ESR) spectra carried out at different temperatures show isotropic signals with a g value of 2.00(1). The thermal evolution of the intensity of the ESR signals indicates the existence of antiferromagnetic interactions for the Fe(III) phase. The magnetic susceptibility data of the Cr(III) and V(III) compounds show antiferromagnetic couplings. The J-exchange parameters of the Fe(III) and Cr(III) compounds have been calculated by using a model for a triangular spin ladder chain. The values are J1 = -1.63(1) K and J2 = -0.87(2) K with g = 2.02 for the Fe(III) phase and J(1) = -0.56(2) K and J2 = -0.40(2) K with g = 1.99 for the Cr(III) compound. In the case of the V(III) phase, the fit has been performed considering a linear chain with the magnetic parameters D = 2.5 cm(-1) and J = -1.15(1) K.