Paul Goddard

Abstract:

Gaining control of the building blocks of magnetic materials and thereby achieving particular characteristics will make possible the design and growth of bespoke magnetic devices. While progress in the synthesis of molecular materials, and especially coordination polymers, represents a significant step towards this goal, the ability to tune the magnetic interactions within a particular framework remains in its infancy. Here we demonstrate a chemical method which achieves dimensionality selection via preferential inhibition of the magnetic exchange in an S=1/2 antiferromagnet along one crystal direction, switching the system from being quasi-two- to quasi-one-dimensional while effectively maintaining the nearest-neighbor coupling strength.

Abstract:

We present a novel susceptometer with a particularly small spatial footprint and no moving parts. The susceptometer is suitable for use in systems with limited space where magnetic measurements may not have been previously possible, such as in pressure cells and rotators, as well as in extremely high pulsed fields. The susceptometer is based on the proximity detector oscillator, which has a broad dynamic resonant frequency range and has so far been used predominantly for transport measurements. We show that for insulating samples, the resonance frequency behavior as a function of field consists of a magnetoresistive and an inductive component, originating, respectively, from the sensor coil and the sample. The response of the coil is modeled, and upon subtraction of the magnetoresistive component the dynamic magnetic susceptibility and magnetization can be extracted. We successfully measure the magnetization of the organic molecular magnets Cu(H(2)O)(5)(VOF(4))(H(2)O) and [Cu(HF(2))(pyz)(2)]BF(4) in pulsed magnetic fields and by comparing the results to that from a traditional extraction susceptometer confirm that the new system can be used to measure and observe magnetic susceptibilities and phase transitions.

Abstract:

The magnetic ground states of the isostructural double perovskites Ba 2NaOsO6 and Ba2LiOsO6 are investigated with muon-spin relaxation. In Ba2NaOsO6 long-range magnetic order is detected via the onset of a spontaneous muon-spin precession signal below Tc=7.2±0.2K, while in Ba 2LiOsO6 a static but spatially disordered internal field is found below 8 K. A probabilistic argument is used to show from the observed precession frequencies that the magnetic ground state in Ba 2NaOsO6 is most likely to be low-moment (≈0.2μB) ferromagnetism and not canted antiferromagnetism. Ba2LiOsO6 is antiferromagnetic and we find a spin-flop transition at 5.5T. A reduced osmium moment is common to both compounds, probably arising from a combination of spin-orbit coupling and frustration. © 2011 American Physical Society.

Abstract:

[Ni(HF(2))(pyz)(2)]X {pyz = pyrazine; X = PF(6)(-) (1), SbF(6)(-) (2)} were structurally characterized by synchrotron X-ray powder diffraction and found to possess axially compressed NiN(4)F(2) octahedra. At 298 K, 1 is monoclinic (C2/c) with unit cell parameters, a = 9.9481(3), b = 9.9421(3), c = 12.5953(4) Å, and β = 81.610(3)° while 2 is tetragonal (P4/nmm) with a = b = 9.9359(3) and c = 6.4471(2) Å and is isomorphic with the Cu-analogue. Infinite one-dimensional (1D) Ni-FHF-Ni chains propagate along the c-axis which are linked via μ-pyz bridges in the ab-plane to afford three-dimensional polymeric frameworks with PF(6)(-) and SbF(6)(-) counterions occupying the interior sites. A major difference between 1 and 2 is that the Ni-F-H bonds are bent (∼157°) in 1 but are linear in 2. Ligand field calculations (LFT) based on an angular overlap model (AOM), with comparison to the electronic absorption spectra, indicate greater π-donation of the HF(2)(-) ligand in 1 owing to the bent Ni-F-H bonds. Magnetic susceptibility data for 1 and 2 exhibit broad maxima at 7.4 and 15 K, respectively, and λ-like peaks in dχT/dT at 6.2 and 12.2 K that are ascribed to transitions to long-range antiferromagnetic order (T(N)). Muon-spin relaxation and specific heat studies confirm these T(N)'s. A comparative analysis of χ vs T to various 1D Heisenberg/Ising models suggests moderate antiferromagnetic interactions, with the primary interaction strength determined to be 3.05/3.42 K (1) and 5.65/6.37 K (2). However, high critical fields of 19 and 37.4 T obtained from low temperature pulsed-field magnetization data indicate that a single exchange constant (J(1D)) alone is insufficient to explain the data and that residual terms in the spin Hamiltonian, which could include interchain magnetic couplings (J(⊥)), as mediated by Ni-pyz-Ni, and single-ion anisotropy (D), must be considered. While it is difficult to draw absolute conclusions regarding the magnitude (and sign) of J(⊥) and D based solely on powder data, further support offered by related Ni(II)-pyz compounds and our LFT and density-functional theory (DFT) results lead us to a consistent quasi-1D magnetic description for 1 and 2.

Abstract:

The first molecular material with the coexistence of ferromagnetism, metal-like conductivity, and chirality has been prepared using an organic/inorganic approach. In this case, a two-dimensional packing of chiral organic radical cations (responsible for both the electrical conductivity and optical activity) was assembled with a layered bimetallic oxalate-based anionic network (responsible for the magnetic properties). Shubnikov-de Haas oscillations confirmed the presence of a Fermi surface even when the transport properties suggested "insulating"-type behavior at very low temperatures.