Elisabeth S. Knowles

Persistent Photoinduced Magnetism in Heterostructures of Prussian Blue Analogues

Heterostructured ABA thin films consisting of two different Prussian blue analogues, where A is a ferromagnet and B is a photoinducible ferrimagnet, have been fabricated for the first time. This novel arrangement allows the magnetization to be decreased by irradiation with white light and significantly increases the ordering temperature of the photoinduced magnetism from 18 to 75 K.

Photoinduced Magnetism in Core/Shell Prussian Blue Analogue Heterostructures of KjNik[Cr(CN)6]l·nH2O with RbaCob[Fe(CN)6]c·mH2O

Core/shell and core/shell/shell particles comprised of the Prussian blue analogues K(j)Ni(k)[Cr(CN)(6)](l)·nH(2)O (A) and Rb(a)Co(b)[Fe(CN)(6)](c)·mH(2)O (B) have been prepared for the purpose of studying persistent photoinduced magnetization in the heterostructures. Synthetic procedures have been refined to allow controlled growth of relatively thick (50-100 nm) consecutive layers of the Prussian blue analogues while minimizing the mixing of materials at the interfaces. Through changes in the order in which the two components are added, particles with AB, ABA, BA, and BAB sequences have been prepared. The two Prussian blue analogues were chosen because B is photoswitchable, and A is ferromagnetic with a relatively high magnetic ordering temperature, ~70 K, although it is not known to exhibit photoinduced changes in its magnetic properties. Magnetization measurements on the heterostructured particles performed prior to irradiation show behavior characteristic of the individual components. On the other hand, after irradiation with visible light, the heterostructures undergo persistent photoinduced changes in magnetization associated with both the B and A analogues. The results suggest that structural changes in the photoactive B component distort the normally photoinactive A component, leading to a change in its magnetization.

Magnetodielectric coupling of infrared phonons in single-crystal Cu2OSeO3

Reflection and transmission as a function of temperature (5-300 K) have been measured on a single crystal of the magnetoelectric ferrimagnetic compound Cu2OSeO3 utilizing light spanning the far infrared to the visible portions of the electromagnetic spectrum. The complex dielectric function and optical properties were obtained via Kramers-Kronig analysis and by fits to a Drude-Lortentz model. The fits of the infrared phonons show a magnetodielectric effect near the transition temperature (T-c similar to 60 K). Assignments to strong far-infrared phonon modes have been made, especially those exhibiting anomalous behavior around the transition temperature.

Metal Monophosphonates M{(2-C5H4NO)CH2PO3}(H2O)2 (M = Co, Ni, Mn, Cd): Synthesis, Structure, and Magnetism

Four isostructural metal monophosphonates, M{(2-C(5)H(4)NO)CH(2)PO(3)}(H(2)O)(2) with M = Co (1), Ni (2), Mn (3), and Cd (4), were synthesized and structurally characterized. These compounds show a double-chain structure in which the M(2)(μ-O)(2) dimers are connected by O-P-O bridges. The magnetic responses of 1-3 were investigated over a wide range of magnetic fields (up to 10 T) and temperatures (down to 50 mK). Except for 4, which is weakly diamagnetic from 2 K to room temperature, the dominant magnetic interactions are antiferromagnetic. Isothermal magnetic field sweeps at 50 mK provide signatures in the magnetic responses that are associated with antiferromagnetic to field-induced fully polarized (magnetically saturated) transitions. Analysis of the magnetic data indicates that 1 and 2 form magnetic dimer-like clusters with weak dimer-dimer interactions present. Contrastingly, the magnetic interactions present in 3 are significantly weaker, so a definitive description of the magnetism of this compound is elusive.

Synthesis and Size Control of Iron(II) Hexacyanochromate(III) Nanoparticles and the Effect of Particle Size on Linkage Isomerism

The controlled synthesis of monodisperse nanoparticles of the cubic Prussian blue analogue iron(II) hexacyanochromate(III) is reported along with a kinetic study, using cyanide stretching frequencies, showing the variations of the activation energy (E(a)) of the linkage isomerism as a function of the particle size. Highly reproducible, cubic-shaped iron(II) hexacyanochromate(III) nanocrystals, with sizes ranging from 2 to 50 nm, are synthesized using a microemulsion technique, whereas a bulk synthesis yields nonuniform less monodisperse particles with sizes greater than 100 nm. Monitoring the cyanide stretching frequency with FTIR spectroscopy shows that the rate of isomerization is faster for smaller particles. Moreover, a kinetic analysis at different temperatures (255 K ≤ T ≤ 321 K) gives insight into the evolution of E(a) with the particle size. Finally, time-dependent powder X-ray diffraction and net magnetization confirm the FTIR observations. The data are interpreted within the concept of a simple two-component model with different activation energies for structures near the surface of the solid and within the bulk.

Magnetic neutron scattering of thermally quenched K-Co-Fe Prussian blue analog photomagnet

Magnetic order in the thermally quenched photomagnetic Prussian blue analogue coordination polymer K0.27Co[Fe(CN)6]0.73[D2O6]0.27-1.42D2O has been studied down to 4 K with unpolarized and polarized neutron powder diraction as a function of applied magnetic eld. Analysis of the data allows the onsite coherent magnetization of the Co and Fe spins to be established. Specically, magnetic elds of 1 T and 4 T induce moments parallel to the applied eld, and the sample behaves as a ferromagnet with a wandering axis.