A soluble molecular analogue of photoresponsive Co/Fe Prussian blues is described within this report. As judged via a variety of spectroscopic, magnetic, and crystallographic methods, electron transfer within the octanuclear complex (below 250 K) converts paramagnetic red crystals into green diamagnetic ones. The color and magnetic changes are associated with the transformation of FeIIILS-CN-CoIIHS units into FeIILS-CN-CoIIILS fragments in manner that is identical to that found for the An[Co(OH2)(6-6m)][Fe(CN)6]m.xH2O (An = alkali metal cation) family of three-dimensional Prussian blues. Moreover, this intramolecular electron transfer can be quantitatively circumvented via rapid thermal quenching and reversed via simple white light irradiation at low temperatures. Remarkably the data suggests that thermally or photoinduced paramagnetic metastable phases are identical and exhibit long relaxation times that approach 10 years at 120 K.
The transformation of ≤4 nm equiatomic FePt nanoparticles from the disordered cubic A1 to the ordered tetragonal L1 0 phase was studied by means of high-resolution transmission electron microscopy coupled with in situ heating experiments. In accordance with ex situ annealing experiments, a transition temperature of around 500°C was determined. Diffusion is enhanced at surfaces and plays a dominant role in the ordering process. Hence, the ordering of the crystallographic structure starts at the surface of the nanoparticles and propagates toward their center, resulting in complete ordering within some minutes, for temperatures above 600°C. Unlike the generally assumed lower limit of ordering (3.5 nm), we demonstrate that ultrasmall (less than 3 nm) FePt nanoparticles can also be fully transformed to the L1 0 phase. The well-controlled and precise stoichiometry (Fe 50 at.% Pt 50 at.% ) and the homogeneous composition of these particles both play a major role in their successful phase transformation.
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