Origin of the ESR spectrum in the Prussian Blue analogue RbMn[Fe(CN)6]*H2O

We present an ESR study at excitation frequencies of 9.4 GHz and 222.4 GHz of powders and single crystals of a Prussian Blue analogue (PBA), RbMn[Fe(CN)6]*H2O in which Fe and Mn undergoes a charge transfer transition between 175 and 300 K. The ESR of PBA powders, also reported by Pregelj et al. (JMMM, 316, E680 (2007)) is assigned to cubic magnetic clusters of Mn2+ ions surrounding Fe(CN)6 vacancies. The clusters are well isolated from the bulk and are superparamagnetic below 50 K. In single crystals various defects with lower symmetry are also observed. Spin-lattice relaxation broadens the bulk ESR beyond observability. This strong spin relaxation is unexpected above the charge transfer transition and is attributed to a mixing of the Mn3+ - Fe2+ state into the prevalent Mn2+ - Fe3+ state.Comment: 5 pages, 4 figures, submitted to PR

Bulk and surface switching in Mn-Fe-based Prussian Blue Analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.Comment: 12 pages, 8 figure

Interplay between the Charge Transport Phenomena and the Charge-Transfer Phase Transition in RbxMn[Fe(CN)6]y · zH2O

Charge transport and dielectric measurements were carried out on compacted powder and single-crystal samples of bistable RbxMn[Fe(CN)6]y · zH2O in the two valence-tautomeric forms (MnIIFeIII and MnIIIFeII) as a function of temperature (120-350 K) and frequency (10-2-106 Hz). The complex conductivity data reveal universal conductivity behavior and obey the Barton-Nakajima-Namikawa relationship. The charge transport is accompanied by dielectric relaxation that displays the same thermal activation energy as the conductivity. Surprisingly, the activation energy of the conductivity was found very similar in the two valence-tautomeric forms (∼0.55 eV), and the conductivity change between the two phases is governed mainly by the variation of the preexponential factor in each sample. The phase transition is accompanied by a large thermal hysteresis of the conductivity and the dielectric constant. In the hysteresis region, however, a crossover occurs in the charge transport mechanism at T < ∼220 K from an Arrhenius-type to a varying activation energy behavior, conferring an unusual “double-loop” shape to the hysteresis

Electric-field-induced charge-transfer phase transition: a promising approach toward electrically switchable devices

Much research has been directed toward the development of electrically switchable optical materials for applications in memory and display devices. Here we present experimental evidence for an electric-field-induced charge-transfer phase transition in two cyanometalate complexes: Rb₀․₈Mn-[Fe(CN)₆]₀․₉₃•1.62H₂O and Co₃[W(CN)₈]₂(pyrimidine)₄•6H₂O, involving changes in their magnetic, optical, and electronic properties as well. Application of an electric field above a threshold value and within the thermal hysteresis region leads to a transition from the high- to the low-temperature phase in these compounds. A model is proposed to explain the main observations on the basis of a para-ferroelectric transition. Our observations suggest that this new concept of electrical switching, based on materials exhibiting charge-transfer phase transitions with large thermal hysteresis loops, may open up doors for novel electro-optical devices

Facile method to synthesize Na-enriched Na1+xFeFe(CN)6 frameworks as cathode with superior electrochemical performance for sodium-ion batteries

Different Na-enriched Na1+xFeFe(CN)6 samples can be synthesized by a facile one-step method, utilizing Na4Fe(CN)6 as the precursor in a different concentration of NaCl solution. As-prepared samples were characterized by a combination of synchrotron X-ray powder diffraction (S-XRD), Mössbauer spectroscopy, Raman spectroscopy, magnetic measurements, thermogravimetric analysis, X-ray photoelectron spectroscopy, and inductively coupled plasma analysis. The electrochemical results show that the Na1.56Fe[Fe(CN)6]·3.1H2O (PB-5) sample shows a high specific capacity of more than 100 mAh g-1 and excellent capacity retention of 97% over 400 cycles. The details structural evolution during Na-ion insertion/extraction processes were also investigated via in situ synchrotron XRD. Phase transition can be observed during the initial charge and discharge process. The simple synthesis method, superior cycling stability, and cost-effectiveness make the Na-enriched Na1+xFe[Fe(CN)6] a promising cathode for sodium-ion batteries