A structural and Mössbauer study of complexes with Fe(2)(micro-O(H))(2) cores: stepwise oxidation from Fe(II)(micro-OH)(2)Fe(II) through Fe(II)(micro-OH)(2)Fe(III) to Fe(III)(micro-O)(micro-OH)Fe(III).

Dinuclear non-heme iron clusters containing oxo, hydroxo, or carboxylato bridges are found in a number of enzymes involved in O(2) metabolism such as methane monooxygenase, ribonucleotide reductase, and fatty acid desaturases. Efforts to model structural and/or functional features of the protein-bound clusters have prompted the preparation and study of complexes that contain Fe(micro-O(H))(2)Fe cores. Here we report the structures and spectroscopic properties of a family of diiron complexes with the same tetradentate N4 ligand in one ligand topology, namely [(alpha-BPMCN)(2)Fe(II)(2)(micro-OH)(2)](CF(3)SO(3))(2) (1), [(alpha-BPMCN)(2)Fe(II)Fe(III)(micro-OH)(2)](CF(3)SO(3))(3) (2), and [(alpha-BPMCN)(2)Fe(III)(2)(micro-O)(micro-OH)](CF(3)SO(3))(3) (3) (BPMCN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane). Stepwise one-electron oxidations of 1 to 2 and then to 3 demonstrate the versatility of the Fe(micro-O(H))(2)Fe diamond core to support a number of oxidation states with little structural rearrangement. Insight into the electronic structure of 1, 2', and 3 has been obtained from a detailed Mössbauer investigation (2' differs from 2 in having a different complement of counterions). Mixed-valence complex 2' is ferromagnetically coupled, with J = -15 +/- 5 cm(-)(1) (H = JS(1).S(2)). For the S = (9)/(2) ground multiplet we have determined the zero-field splitting parameter, D(9/2) = -1.5 +/- 0.1 cm(-)(1), and the hyperfine parameters of the ferric and ferrous sites. For T < 12 K, the S = (9)/(2) multiplet has uncommon relaxation behavior. Thus, M(S) = -(9)/(2) <--> M(S) = +(9)/(2) ground state transition is slow while deltaM(S) = +/-1 transitions between equally signed M(S) levels are fast on the time scale of Mössbauer spectroscopy. Below 100 K, complex 2' is trapped in the Fe(1)(III)Fe(2)(II) ground state; above this temperature, it exhibits thermally assisted electron hopping into the state Fe(1)(II)Fe(2)(III). The temperature dependence of the isomer shifts was corrected for second-order Doppler shift, obtained from the study of diferrous 1. The resultant true shifts were analyzed in a two-state hopping model. The diferric complex 3 is antiferromagnetically coupled with J = 90 +/- 15 cm(-)(1), estimated from a variable-temperature Mössbauer analysis.

Aqua Ions. 2. Structural manifestations of the Jahn-Teller effect in the beta-alums.

Variable-temperature single-crystal neutron diffraction structures of the alums CsM(III)(SO(4))(2).12D(2)O, where M(III) = Ti, V, Mn, and Ga, are reported. Structural differences are highlighted by the titanium and manganese alums, which undergo cubic (Pathremacr;) to orthorhombic (Pbca) phase transitions at approximately 13 and approximately 156 K, respectively. The structural instability exhibited by these salts is interpreted as arising from cooperative Jahn-Teller interactions, and these measurements characterize the structural changes that result from the coupling between the electronic and vibrational states. Although the symmetry changes associated with the phase transformations are analogous for the Ti and Mn alums, the low-temperature geometries of the tervalent hexaaqua cations are markedly different. Whereas the MnO(6) framework is subject to a pronounced tetragonal elongation, changes in the Ti-O bond lengths are very modest; but significant changes in the O-Ti-O bond angles and in the disposition of the coordinated water molecules are identified. The large differences in the transition temperatures and in the low-temperature stereochemistries of the [Ti(OD(2))(6)](3+) and [Mn(OD(2))(6)](3+) cations are related to the sensitivity of the energies of the t(2g) (O(h)) and e(g) (O(h)) orbitals to the various asymmetric vibrations of the hexaaqua complex.

Inelastic neutron scattering on three mixed-valence dodecanuclear polyoxovanadate clusters.

The magnetic exchange interactions in the mixed-valence dodecanuclear polyoxovanadate compounds Na(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(H(2)O)].23H(2)O, Na(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(D(2)O)].16.5D(2)O, and (NHEt(3))(4)[V(IV)(8)V(V)(4)As(III)(8)O(40)(H(2)O)].H(2)O were investigated by an inelastic neutron scattering (INS) study using cold neutrons. In addition, the synthesis procedures and the single-crystal X-ray structures of these compounds have been investigated together with the temperature dependence of their magnetic susceptibilities. The magnetic properties below 100 K can be described by simply taking into account an antiferromagnetically exchange coupled tetramer, consisting of four vanadium(IV) ions. Up to four magnetic transitions between the cluster S = 0 ground state and excited states could be observed by INS. The transition energies and the relative INS intensities could be modeled on the basis of the following exchange Hamiltonian: H(ex) = -2J(12)(xy)[S(1x)S(2x)+ S(3x)S(4x)+ S(1y)S(2y)+ S(3y)S(4y)] - 2J(12)(z)[(S(1z)S(2z)+ S(3z)S(4z)] - 2J(23)(xy)[(S(2x)S(3x)+ S(1x)S(4x)+ S(2y)S(3y)+ S(1y)S(4y)] - 2J(23)(z)[(S(2z)S(3z)+ S(1z)S(4z)]. The following sets of parameters were derived: for Na(4)[V(12)As(8)O(40)(H(2)O)].23H(2)O, J(12)(xy)() = J(12)(z)= -0.80 meV, J(23)(xy) = J(23)(z) = -0.72 meV; for Na(4)[V(12)As(8)O(40)(D(2)O)].16.5D(2)O, J(12)(xy) = J(12)(z) = J(23)(xy) = J(23)(z = -0.78 meV; for (NHEt(3))(4)[V(12)As(8)O(40)(H(2)O)].H(2)O, J(12)(xy) = -0.80 meV, J(12)(z) = -0.82 meV, J(23)(xy)() = -0.67 meV, J(23)(z) = -0.69 meV. This study of the same [V(12)As(8)]-type cluster in three different crystal environments allows us to draw some conclusions concerning the applicability on INS in the area of nondeuterated molecular spin clusters. In addition, the effects of using nondeuterated samples and different sample container shapes for INS were evaluated.

Studies of a nickel-based single-molecule magnet.

A cyclic complex [Ni(12)(chp)(12)(O(2)CMe)(12)(thf)(6)(H(2)O)(6)] (1) has been synthesised and studied (chp=6-chloro-2-pyridonate). Complex 1 exhibits ferromagnetic exchange between the S=1 centres, giving an S=12 spin ground state. Detailed studies demonstrate that it is a single-molecule magnet with an energy barrier of approximately 10 K for reorientation of magnetisation. Resonant quantum tunnelling is also observed. The field between resonances allows accurate measurement of D, which is 0.067 K. Inelastic neutron scattering studies have allowed exchange parameters to be derived accurately, which was impossible from susceptibility data alone. Three exchange interactions are required: two ferromagnetic nearest neighbour interactions of approximately 11 and 2 cm(-1) and an anti-ferromagnetic next nearest neighbour interaction of -0.9 cm(-1).

Competing interactions in the tetranuclear spin cluster [Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O. An inelastic neutron scattering and magnetic study.

The properties of the spin state manifold of the tetranuclear cluster Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O (bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine) are investigated by combining magnetic susceptibility and magnetization measurements with an inelastic neutron scattering (INS) study on an undeuterated sample of Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O. The temperature dependence of the magnetic susceptibility indicates an S = (1)/(2) ground state, which requires antiferromagnetic interactions both between Cr(3+) and Ni(2+) ions and among the Cr(3+) ions. INS reveals potential single-ion anisotropies to be negligibly small and enables an accurate determination of the exchange parameters. The best fit to the experimental energy level diagram is obtained by an isotropic spin Hamiltonian H = J(CrNi)(S(1)().S(4)() + S(2)().S(4)() + S(3)().S(4)()) + J(CrCr)(S(1)().S(2)() + S(1)().S(3)() + S(2)().S(3)()) with J(CrNi) = 1.47 cm(-)(1) and J(CrCr) = 1.25 cm(-)(1). With this model, the experimental intensities of the observed INS transitions as well as the temperature dependence of the magnetic data are reproduced. The resulting overall antiferromagnetic exchange is rationalized in terms of orbital exchange pathways and compared to the situation in oxalato-bridged clusters.

Planar three-coordinate high-spin Fe(II) complexes with large orbital angular momentum: Mössbauer, electron paramagnetic resonance, and electronic structure studies.

Mössbauer spectra of [LFe(II)X](0) (L = beta-diketiminate; X = Cl(-), CH(3)(-), NHTol(-), NHtBu(-)), 1.X, were recorded between 4.2 and 200 K in applied magnetic fields up to 8.0 T. A spin Hamiltonian analysis of these data revealed a spin S = 2 system with uniaxial magnetization properties, arising from a quasi-degenerate M(S) = +/-2 doublet that is separated from the next magnetic sublevels by very large zero-field splittings (3/D/ > 150 cm(-1)). The ground levels give rise to positive magnetic hyperfine fields of unprecedented magnitudes, B(int) = +82, +78, +72, and +62 T for 1.CH(3), 1.NHTol, 1.NHtBu, and 1.Cl, respectively. Parallel-mode EPR measurements at X-band gave effective g values that are considerably larger than the spin-only value 8, namely g(eff) = 10.9 (1.Cl) and 11.4 (1.CH(3)), suggesting the presence of unquenched orbital angular momenta. A qualitative crystal field analysis of g(eff) shows that these momenta originate from spin-orbit coupling between energetically closely spaced yz and z(2) 3d-orbital states at iron and that the spin of the M(S) = +/-2 doublet is quantized along x, where x is along the Fe-X vector and z is normal to the molecular plane. A quantitative analysis of g(eff) provides the magnitude of the crystal field splitting of the lowest two orbitals, /epsilon(yz) - epsilon(2)(z)/ = 452 (1.Cl) and 135 cm(-1) (1.CH(3)). A determination of the sign of the crystal field splitting was attempted by analyzing the electric field gradient (EFG) at the (57)Fe nuclei, taking into account explicitly the influence of spin-orbit coupling on the valence term and ligand contributions. This analysis, however, led to ambiguous results for the sign of epsilon(yz) - epsilon(2)(z). The ambiguity was resolved by analyzing the splitting Delta of the M(S) = +/-2 doublet; Delta = 0.3 cm(-1) for 1.Cl and Delta = 0.03 cm(-)(1) for 1.CH(3). This approach showed that z(2) is the ground state in both complexes and that epsilon(yz) - epsilon(2)(z) approximately 3500 cm(-1) for 1.Cl and 6000 cm(-1) for 1.CH(3). The crystal field states and energies were compared with the results obtained from time-dependent density functional theory (TD-DFT). The isomer shifts and electric field gradients in 1.X exhibit a remarkably strong dependence on ligand X. The ligand contributions to the EFG, denoted W, were expressed by assigning ligand-specific parameters: W(X) to ligands X and W(N) to the diketiminate nitrogens. The additivity and transferability hypotheses underlying this model were confirmed by DFT calculations. The analysis of the EFG data for 1.X yields the ordering W(N(diketiminate)) < W(Cl) < W(N'HR), W(CH(3)) and indicates that the diketiminate nitrogens perturb the iron wave function to a considerably lesser extent than the monodentate nitrogen donors do. Finally, our study of these synthetic model complexes suggests an explanation for the unusual values for the electric hyperfine parameters of the iron sites in the Fe-Mo cofactor of nitrogenase in the M(N) state.