Francis L. Pratt

Organic and molecular magnets

Historically most materials in magnetic applications are based on inorganic materials. Recently, however, organic and molecular materials have begun to show increasing promise. Purely organic ferromagnets, based upon nitronyl nitroxide radicals, show long range magnetic order at very low temperatures in the region of 1 K, while sulfur based radicals show weak ferromagnetism at temperatures up to 36 K. It is also possible to prepare molecule based magnets in which transition metal ions are used to provide the magnetic moment, but organic groups mediate the interactions. This strategy has produced magnetic materials with a large variety of structures, including chains, layered systems and three-dimensional networks, some of which show ordering at room temperature and some of which have very high coercivity. Even if long range magnetic order is not achieved, the spin crossover effect may be observed, which has important applications. Further magnetic materials may be obtained by constructing charge transfer salts, which can produce metallic molecular magnets. Another development is single-molecule magnets, formed by preparing small magnetic clusters. These materials can show macroscopic quantum tunnelling of the magnetization and may have uses as memory devices or in quantum computation applications.

Coexistence of static magnetism and superconductivity in SmFeAsO 1− x F x as revealed by muon spin rotation

The recent observation of superconductivity with critical temperatures (Tc) up to 55 K in the pnictide RFeAsO(1-x)F(x), where R is a lanthanide, marks the first discovery of a non-copper-oxide-based layered high-Tc superconductor. It has raised the suspicion that these new materials share a similar pairing mechanism to the cuprate superconductors, as both families exhibit superconductivity following charge doping of a magnetic parent material. In this context, it is important to follow the evolution of the microscopic magnetic properties of the pnictides with doping and hence to determine whether magnetic correlations coexist with superconductivity. Here, we present a muon spin rotation study on SmFeAsO(1-x)F(x), with x=0-0.30 that shows that, as in the cuprates, static magnetism persists well into the superconducting regime. This analogy is quite surprising as the parent compounds of the two families have rather different magnetic ground states: itinerant spin density wave for the pnictides contrasted with the Mott-Hubbard insulator in the cuprates. Our findings therefore suggest that the proximity to magnetic order and associated soft magnetic fluctuations, rather than strong electronic correlations in the vicinity of a Mott-Hubbard transition, may be the key ingredients of high-Tc superconductors.

Engineering spin propagation across a hybrid organic/inorganic interface using a polar layer

Spintronics has shown a remarkable and rapid development, for example from the initial discovery of giant magnetoresistance in spin valves to their ubiquity in hard-disk read heads in a relatively short time. However, the ability to fully harness electron spin as another degree of freedom in semiconductor devices has been slower to take off. One future avenue that may expand the spintronic technology base is to take advantage of the flexibility intrinsic to organic semiconductors (OSCs), where it is possible to engineer and control their electronic properties and tailor them to obtain new device concepts. Here we show that we can control the spin polarization of extracted charge carriers from an OSC by the inclusion of a thin interfacial layer of polar material. The electric dipole moment brought about by this layer shifts the OSC highest occupied molecular orbital with respect to the Fermi energy of the ferromagnetic contact. This approach allows us full control of the spin band appropriate for charge-carrier extraction, opening up new spintronic device concepts for future exploitation.

Control of the competition between a magnetic phase and a superconducting phase in cobalt-doped and nickel-doped NaFeAs using electron count.

Dinah R. Parker, Matthew J. P. Smith, Tom Lancaster, Andrew J. Steele, Isabel Franke, Peter J. Baker, Francis L. Pratt, Michael J. Pitcher, Stephen J. Blundell, ∗ and Simon J. Clarke † Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, United Kingdom Clarendon Laboratory, University of Oxford, Parks Road, Oxford OX1 3PU, United Kingdom ISIS Facility, STFC-Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, OX11 0QX, United Kingdom (Dated: September 16, 2010)

Strong H...F hydrogen bonds as synthons in polymeric quantum magnets: structural, magnetic, and theoretical characterization of [Cu(HF2)(pyrazine)2]SbF6, [Cu2F(HF)(HF2)(pyrazine)4](SbF6)2, and [CuAg(H3F4)(pyrazine)5](SbF6)2.

Three Cu(2+)-containing coordination polymers were synthesized and characterized by experimental (X-ray diffraction, magnetic susceptibility, pulsed-field magnetization, heat capacity, and muon-spin relaxation) and electronic structure studies (quantum Monte Carlo simulations and density functional theory calculations). [Cu(HF(2))(pyz)(2)]SbF(6) (pyz = pyrazine) (1a), [Cu(2)F(HF)(HF(2))(pyz)(4)](SbF(6))(2) (1b), and [CuAg(H(3)F(4))(pyz)(5)](SbF(6))(2) (2) crystallize in either tetragonal or orthorhombic space groups; their structures consist of 2D square layers of [M(pyz)(2)](n+) that are linked in the third dimension by either HF(2)(-) (1a and 1b) or H(3)F(4)(-) (2). The resulting 3D frameworks contain charge-balancing SbF(6)(-) anions in every void. Compound 1b is a defective polymorph of 1a, with the difference being that 50% of the HF(2)(-) links are broken in the former, which leads to a cooperative Jahn-Teller distortion and d(x(2))(-y(2)) orbital ordering. Magnetic data for 1a and 1b reveal broad maxima in chi at 12.5 and 2.6 K and long-range magnetic order below 4.3 and 1.7 K, respectively, while 2 displays negligible spin interactions owing to long and disrupted superexchange pathways. The isothermal magnetization, M(B), for 1a and 1b measured at 0.5 K reveals contrasting behaviors: 1a exhibits a concave shape as B increases to a saturation field, B(c), of 37.6 T, whereas 1b presents an unusual two-step saturation in which M(B) is convex until it reaches a step near 10.8 T and then becomes concave until saturation is reached at 15.8 T. The step occurs at two-thirds of M(sat), suggesting the presence of a ferrimagnetic structure. Compound 2 shows unusual hysteresis in M(B) at low temperature, although chi vs T does not reveal the presence of a magnetic phase transition. Quantum Monte Carlo simulations based on an anisotropic cubic lattice were applied to the magnetic data of 1a to afford g = 2.14, J = -13.4 K (Cu-pyz-Cu), and J(perpendicular) = -0.20 K (Cu-F...H...F-Cu), while chi vs T for 1b could be well reproduced by a spin-1/2 Heisenberg uniform chain model for g = 2.127(1), J(1) = -3.81(1), and zJ(2) = -0.48(1) K, where J(1) and J(2) are the intra- and interchain exchange couplings, respectively, which considers the number of magnetic nearest-neighbors (z). The M(B) data for 1b could not be satisfactorily explained by the chain model, suggesting a more complex magnetic structure in the ordered state and the need for additional terms in the spin Hamiltonian. The observed variation in magnetic behaviors is driven by differences in the H...F hydrogen-bonding motifs.

Coexistence of magnetic fluctuations and superconductivity in the pnictide high temperature superconductor SmFeAsO1-xFx measured by muon spin rotation.

Muon spin rotation experiments were performed on the pnictide high temperature superconductor SmFeAsO1-xFx with x=0.18 and 0.3. We observed an unusual enhancement of slow spin fluctuations in the vicinity of the superconducting transition which suggests that the spin fluctuations contribute to the formation of an unconventional superconducting state. An estimate of the in-plane penetration depth lambda ab(0)=190(5) nm was obtained, which confirms that the pnictide superconductors obey an Uemura-style relationship between Tc and lambda ab(0);(-2).

Experimentally determining the exchange parameters of quasi-two-dimensional Heisenberg magnets

Though long-range magnetic order cannot occur at temperatures T > 0 in a perfect two-dimensional (2D) Heisenberg magnet, real quasi-2D materials will invariably possess nonzero inter-plane coupling J? driving the system to order at elevated temperatures. This process can be studied using quantum Monte Carlo calculations. However, it is difficult to test the results of these calculations experimentally since for highly anisotropic materials in which the in-plane coupling is comparable with attainable magnetic fields J? is necessarily very small and inaccessible directly. In addition, because of the large anisotropy, the Neel temperatures are low and difficult to determine from thermodynamic measurements. Here, we present an elegant method of assessing the calculations via two independent experimental probes: pulsed-field magnetization in fields of up to 85T, and muon-spin rotation.

Compositional Control of the Superconducting Properties of LiFeAs

The response of the superconducting state and crystal structure of LiFeAs to chemical substitutions on both the Li and the Fe sites has been probed using high-resolution X-ray and neutron diffraction measurements, magnetometry, and muon-spin rotation spectroscopy. The superconductivity is extremely sensitive to composition: Li-deficient materials (Li(1-y)Fe(1+y)As with Fe substituting for Li) show a very rapid suppression of the superconducting state, which is destroyed when y exceeds 0.02, echoing the behavior of the Fe(1+y)Se system. Substitution of Fe by small amounts of Co or Ni results in monotonic lowering of the superconducting transition temperature, T(c), and the superfluid stiffness, rho(s), as the electron count increases. T(c) is lowered monotonically at a rate of 10 K per 0.1 electrons added per formula unit irrespective of whether the dopant is Co and Ni, and at higher doping levels superconductivity is completely suppressed. These results and the demonstration that the superfluid stiffness in these LiFeAs-derived compounds is higher than in all of the iron pnictide materials underlines the unique position that LiFeAs occupies in this class.

Frustration of Magnetic and Ferroelectric Long-Range Order in Bi2Mn4/3Ni2/3O6

The slight incommensurate modulation of the structure of Bi(2)Mn(4/3)Ni(2/3)O(6) is sufficient to suppress the electrical polarization which arises in commensurate treatments of the structure, due to antiferroelectric coupling of local polar units of over 900 A(3). The incommensurate structure is produced by the competition between ferroelectric Bi lone pair-driven A site displacement, chemical order of Mn and Ni on the B site, and both charge and orbital order at these transition metals. The interplay between the frustrated polar Bi displacements and the frustrated spin order at the B site, induced by positional disorder, produces magnetodielectric coupling between the incommensurately modulated lattice and the spin-glass-like ground state with an unusual relationship between the magnetocapacitance and the applied field.

Two Homometallic Antiferromagnets Based on Oxalato-Bridged Honeycomb Assemblies: (A)2[MII2(C2O4)3] (A = Ammonium Salt Derived from Diethylenetriamine; MII = Fe2+, Co2+)

Oxalato-bridged divalent homometallic compounds A(2)[M(II)(2)(C(2)O(4))(3)] (M(II) = Fe(2+) (1), Co(2+) (2)) were obtained by a solvothermal method. They consist of honeycomb anions and cations, that is, the 5-oxo-1,4,7-triazabicyclo[4.3.0]non-6-en-7-yl ammonium ion (hereafter abbreviated as A(1)) in 1 and the 2-(2,3-dioxo-1-piperazinyl)eth-1-yl ammonium ion (hereafter abbreviated as A(2)) in 2, which were generated from in situ reactions of diethylenetriamine (DETA) with oxalic acid catalyzed by the metal ions and yielded two compounds with different cell parameters: a = 17.2224(4)A, b = 9.3151(2)A, c = 15.1518(4)A, beta = 95.767(1) degrees , V = 2418.5(1)A(3), and Z = 4, C2/c for 1 and a = 9.6924(2)A, b = 15.8325(4)A, c = 17.2995(4)A, beta = 95.144(1) degrees , V = 2644.0(1)A(3), Z = 4, and P2(1)/n for 2. A(1) points its carbonyl group to the pocket of the honeycomb network. A(2) forms a helical chain around the anion layers through hydrogen bonds along the 2(1) axis, and the crystal remains achiral due to the existence of the inversion symmetry. The methanol molecules occupy the holes situated between A(2) and the oxalate network in 2. The distance between two anion layers in 1 was shorter than in 2 due to the template effect of the ammonium salts. In the anion layers, the hexagonal rings are elongated along the a axis in 1 and 2. There are interactions as hydrogen bonds between the cation and anion and between cations. A broad maximum observed in the temperature-dependent susceptibility curve shows antiferromagnetic interactions between paramagnetic ions. The antiferromagnetic ordering at 28 K in 1 and 21 K in 2 was confirmed by ac suspceptibility and specific heat measurements. Hysteresis loops with a coercive field of 17 Oe in 1 and 2300 Oe in 2 were observed at 2 K.