Photoinduced Magnetism in Core/Shell Prussian Blue Analogue Heterostructures of K_jNi_k[Cr(CN)₆]_l·nH₂O with Rb_aCo_b[Fe(CN)₆]_c·mH₂O

Abstract

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.

Layer-by-layer Nanoarchitectonics: Invention, Innovation, and Evolution

“…Dumont et al have successfully synthesized coreshell and coreshellshell particles composed of two different Prussian blue (PB) analogues utilizing an optimized layer-by-layer growth. 303 Recently, hollow particles with microporous crystalline shells have attracted interest because they have large storage capacities and allow guest species to pass easily into their internal cavities. Hollow PB analogue nanocubes can be prepared by chemically dissolving the cores of coreshell heterostructures as a sacrificial removable template.…”

High-pressure neutron scattering of the magnetoelastic Ni-Cr Prussian blue analog

“…'s 1(b) which is in accord with previous TEM reports from similar synthesis. 26 Refined positions of atoms within the unit cell are reported in Table I for the NPD is then used for magnetic scattering. The differences between XPS and diffraction chemical formulas might be representative of experimental uncertainty within this unstoichiometric compound, but we also note that XPS might be probing a surface chemical formula, which is the reason that we do not co-refine XPS and XRD.…”

Electrochromic bilayers of Prussian blue and its Cr analogue

“…A wealth of heterostructures exist which contain PB in combination with other materials, such as dye-sensitised titania 3 and conductive polymers. 4,5 There have also been a number of studies that employ multiple Prussian blue analogues (PBAs) to create heterostructures in the form of thin films or nanoparticles to study photoinduced magnetism 6,7 and magneto-structural effects. [8][9][10] Their electrochemical 11 and optical 12 properties have also been studied.…”

“…These measurements open up the possibility to control the optical properties of multilayered functional materials and the layer-sensitivity enables ground-breaking studies of charge-transfer processes in important multilayers and heterostructures with applications for solar cells, spintronics and photonic devices. 6 ] 4À , which subsequently reacts with Fe 3+ cations at the electrode surface. The product is the insoluble PB created on the FeCr electrode surface.…”