Neutron Studies of a High Spin Fe-19 Molecular Nanodisc

MAGNETOCHEMISTRY 7:6 (2021) ARTN 74

Authors:

Francis L Pratt, Tatiana Guidi, Pascal Manuel, Christopher E Anson, Jinkui Tang, Stephen J Blundell, Annie K Powell

Abstract:

The molecular cluster system [Fe19 (metheidi)10 (OH)14O6 (H2O)12 ]NO3·24H2O, abbrevi-ated as Fe19, contains nineteen Fe(III) ions arranged in a disc-like structure with the total spin S = 35/2. For the first order, it behaves magnetically as a single molecule magnet with a 16 K anisotropy barrier. The high spin value enhances weak intermolecular interactions for both dipolar and superexchange mechanisms and an eventual transition to antiferromagnetic order occurs at 1.2 K. We used neutron diffraction to determine both the mode of ordering and the easy spin axis. The observed ordering was not consistent with a purely dipolar driven order, indicating a significant contribution from intermolecular superexchange. The easy axis is close to the molecular Fe1–Fe10 axis. Inelastic neutron scattering was used to follow the magnetic order parameter and to measure the magnetic excitations. Direct transitions to at least three excited states were found in the 2 to 3 meV region. Measurements below 0.2 meV revealed two low energy excited states, which were assigned to S = 39/2 and S = 31/2 spin states with respective excitation gaps of 1.5 and 3 K. Exchange interactions operating over distances of order 10 Å were determined to be on the order of 5 mK and were eight-times stronger than the dipolar coupling.

The Internal Field in a Ferromagnetic Crystal with Chiral Molecular Packing of Achiral Organic Radicals

MAGNETOCHEMISTRY 7:5 (2021) ARTN 71

Authors:

Stephen J Blundell, Tom Lancaster, Peter J Baker, Francis L Pratt, Daisuke Shiomi, Kazunobu Sato, Takeji Takui

Abstract:

The achiral organic radical dinitrophenyl nitronyl nitroxide crystallizes in two enan-tiomorphs, both being chiral tetragonal space groups that are mirror images of each other. Muon-spin rotation experiments have been performed to study the magnetic properties of these crystals and demonstrate that long-range magnetic order is established below a temperature of 1.10(1) K. Two oscil-latory components are detected in the muon data, which show two different temperature dependences.

Magnetic and Structural Properties of Organic Radicals Based on Thienyl- and Furyl-Substituted Nitronyl Nitroxide

MAGNETOCHEMISTRY 7:5 (2021) ARTN 62

Authors:

Tadashi Sugano, Stephen J Blundell, William Hayes, Hatsumi Mori

Abstract:

Magnetic properties of organic radicals based on thienyl-and furyl-substituted nitronyl nitroxide (NN) and iminonitroxide (IN) were investigated by measuring the temperature dependence of the magnetization. The magnetic behavior of 2-benzo[b]thienyl NN (2-BTHNN) is interpreted in terms of the two-magnetic-dimer model, in which one dimer exhibits ferromagnetic (FM) intermolecular interaction and the other dimer shows antiferromagnetic (AFM) interaction. The existence of two dimers in 2-BTHNN is supported by crystal structure analysis. The magnetic behaviors of 2-bithienyl NN, 4-(2′-thienyl)phenyl NN (2-THPNN), 2-and 3-furyl NN, 2-benzo[b]furyl NN, and 3-benzo[b]thienyl IN are also reported. The one-dimensional alternating AFM nature observed in 2-THPNN is consistent with its crystal structure.

Inhomogeneous superconductivity in LuxZr1-xB12 dodecaborides with dynamic charge stripes

PHYSICAL REVIEW B 103:10 (2021) ARTN 104515

Authors:

A Azarevich, A Bogach, V Glushkov, S Demishev, A Khoroshilov, K Krasikov, V Voronov, N Shitsevalova, V Filipov, S Gabani, K Flachbart, A Kuznetsov, S Gavrilkin, K Mitsen, Sj Blundell, Ne Sluchanko

Abstract:

We have studied the normal and superconductive state characteristics (resistivity, Hall coefficient, heat capacity, and magnetization) of model strongly correlated electronic systems LuxZr1-xB12 with cooperative Jahn-Teller instability of the boron rigid cage and with dynamic charge stripes. It was found that these metals are s-wave dirty limit superconductors with a small mean free path of charge carriers l=5-140Å and with a Cooper pair size changing nonmonotonously in the range 450-4000 Å. The parent ZrB12 and LuB12 borides are type-I superconductors, and Zr to Lu substitution induces a type-I to type-II phase transition providing a variation of the Ginzburg-Landau-Maki parameter in the limits 0.65≤κ1,2≤6. We argue in favor of the two-band scenario of superconductivity in LuxZr1-xB12 with gap values Δ1∼14K and Δ2∼6-8K, with pairing corresponding to strong coupling limit (λe-ph∼1) in the upper band, and to weak coupling (λe-ph∼0.1-0.4) in the lower one. A pseudogap Δps-gap∼60-110K is observed in LuxZr1-xB12 above Tc. We discuss also the possibility of anisotropic single-band superconductivity with stripe-induced both pair breaking and anisotropy, and analyze the origin of a unique enhanced surface superconductivity detected in these model compounds.

Magnetic ground state of the one-dimensional ferromagnetic chain compounds M(NCS)(2)(thiourea)(2) (M = Ni, Co)

PHYSICAL REVIEW MATERIALS 5:3 (2021) 34401

Authors:

Spm Curley, R Scatena, Rc Williams, Pa Goddard, P Macchi, Tj Hicken, T Lancaster, F Xiao, Sj Blundell, V Zapf, Jc Eckert, Eh Krenkel, Ja Villa, Ml Rhodehouse, Jl Manson

Abstract:

The magnetic properties of the two isostructural molecule-based magnets - Ni(NCS)2(thiourea)2, S=1 [thiourea=SC(NH2)2] and Co(NCS)2(thiourea)2, S=3/2 - are characterized using several techniques in order to rationalize their relationship with structural parameters and to ascertain magnetic changes caused by substitution of the spin. Zero-field heat capacity and muon-spin relaxation measurements reveal low-temperature long-range ordering in both compounds, in addition to Ising-like (D<0) single-ion anisotropy (DCo∼-100 K, DNi∼-10 K). Crystal and electronic structure, combined with dc-field magnetometry, affirm highly quasi-one-dimensional behavior, with ferromagnetic intrachain exchange interactions JCo≈+4 K and JNi∼+100 K and weak antiferromagnetic interchain exchange, on the order of J′∼-0.1 K. Electron charge- and spin-density mapping reveals through-space exchange as a mechanism to explain the large discrepancy in J-values despite, from a structural perspective, the highly similar exchange pathways in both materials. Both species can be compared to the similar compounds MCl2(thiourea)4, M = Ni(II) (DTN) and Co(II) (DTC), where DTN is known to harbor two magnetic-field-induced quantum critical points. Direct comparison of DTN and DTC with the compounds studied here shows that substituting the halide Cl- ion for the NCS- ion results in a dramatic change in both the structural and magnetic properties.