Olivia N. Risset

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.

Synergistic photomagnetic effects in coordination polymer heterostructure particles of Hofmann-like Fe(4-phenylpyridine)2[Ni(CN)4]·0.5H2O and K0.4Ni[Cr(CN)6]0.8·nH2O

New nanometer scale heterostructure particles of the two-dimensional Hofmann-like Fe(ii) spin-crossover network, Fe(phpy)2[Ni(CN)4]·0.5H2O {phpy = 4-phenylpyridine}, and the Prussian blue analogue K0.4Ni1.0[Cr(CN)6]0.8·nH2O (NiCr-PBA) have been developed, exhibiting synergistic photomagnetic effects, whereby the LIESST (light-induced electron spin-state trapping) effect in the Hofmann-like material induces a magnetization change in the NiCr-PBA. A variety of microscopic and spectroscopic techniques demonstrate the heterogeneous growth of the NiCr-PBA on the Hofmann seed particles and show the Hofmann compound retains its thermal and photoinduced spin transition properties in the heterostructure. The photoinduced magnetization change in the NiCr-PBA network arises from coupling of the two lattices despite dissimilar structure types. Isothermal magnetization minor hysteresis loop studies at 5 K show light absorption leads to changes in the local anisotropy of NiCr-PBA magnetic domains, providing direct evidence for a general magnetomechanical mechanism of light-switchable magnetism in coordination polymer heterostructures combining a photoactive material with a magnet.

Antiferromagnetic ordering in MnF(salen)

Antiferromagnetic order at [Formula: see text] K has been identified in Mn(III)F(salen), salen  =  H14C16N2O2, an S  =  2 linear-chain system. Using single crystals, specific heat studies performed in magnetic fields up to 9 T revealed the presence of a field-independent cusp at the same temperature where (1)H NMR studies conducted at 42 MHz observed dramatic changes in the spin-lattice relaxation time, T 1, and in the linewidths. Low-field (less than 0.1 T) magnetic susceptibility studies of single crystals and randomly-arranged microcrystalline samples reveal subtle features associated with the transition.