Metal-to-metal electron transfer and magnetic interactions in a mixed-valence Prussian Blue analogue

Bhattacharjee, A.; Saha, Sandip; Koner, Subratanath; Ksenofontov, Vadim; Reiman, S.; Gütlich, Philipp

doi:10.1016/j.jmmm.2005.09.004

Cited by 14 publications

(8 citation statements)

References 45 publications

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“…During the anodic sweep, MnHF showed a faradaic process at 0.52 V vs Ag/AgCl (thin line), which was attributed to an oxidation from Fe II (t 2g 6 e g 0 ) to Fe III (t 2g 5 e g 0 ) due to spontaneous electron hopping from Mn to Fe through the cyanide linker, as reported . This behavior could be explained by the metal to metal charge transfer mechanism, as reported for manganese PBA …”

Section: Resultssupporting

confidence: 72%

Enhancement of Stability by Positive Disruptive Effect on Mn–Fe Charge Transfer in Vacancy-Free Mn–Co Hexacyanoferrate Through a Charge/Discharge Process in Aqueous Na-Ion Batteries

et al. 2018

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Several materials have been studied as electrodes for aqueous batteries that use sodium as alkali ion; these include Prussian blue analogue or hexacyanoferrates. The inhibition or disruption on metal−metal charge transfer plays an important role for improving electrochemical stability of the material. The stability improvement is achieved when two external metals are coordinated to N ends in the Na-rich hexacyanoferrates. Additionally, the presence of vacancies in the material is another important factor that influences its stability. In this study, Na x Co 1−y Mn y [Fe(CN) 6 ] has been synthesized at different Mn/Co ratios by precipitation using citrate as a chelating agent to obtain a material without vacancies. Its electrochemical behavior during redox processes and the correlation with the electronic interaction between external metal sites in the framework through the interaction of spins have been studied too. To discuss the effect of the presence of [Fe(CN) 6 ] nvacancies on the electrochemical process, we synthesized a material without citrate for obtaining materials with low ferrocyanide vacancies. The vacancy-free Co 0.55 Mn 0.45 HF versus n-CoMnHF, were compared in this work. These studies reveal that manganese hexacyanoferrate is unstable. The partial substitution of Co by Mn modifies the metals spin ordering and consequently, the interaction between metals coordinated to N in the cyanide linker. Such partial substitution, with a Mn/Co ratio of 1:1 (Co 0.55 Mn 0.45 HF), improves the electrochemical stability and enhances the discharged potential as well. On the other hand, when vacancies are present, the n-CoMnHF compound showed a decrease in its crystallinity as well as in its external metal interaction. Both changes may be due to the presence of coordinated water, which modifies electrochemical performance. A spontaneous hopping from Mn to Fe during oxidation in n-CoMnHF was detected, but this phenomenon was disrupted in Co 0.55 Mn 0.45 HF. Such charge transfer inhibition was associated with the modification of electron delocalization on Fe (LS); which was caused by the external metals; mainly by Co.

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Section: Resultssupporting

confidence: 72%

Enhancement of Stability by Positive Disruptive Effect on Mn–Fe Charge Transfer in Vacancy-Free Mn–Co Hexacyanoferrate Through a Charge/Discharge Process in Aqueous Na-Ion Batteries

et al. 2018

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“…In a PBA with general formula A x [B(CN) 6 ] y ÁzH 2 O, the exchange constant J may be expressed as 42,46,47…”

Section: Polycrystallinementioning

confidence: 99%

“…In the CN-bridged molecular magnets, such kind of magnetic field dependent phase transitions have been also reported. Good 42 etc. The magnetic structures of these compounds can be described as AF-coupled stacks of ferrimagnetic/ferromagnetic layers, and phase transitions occur due to a competition between the intra and inter-layer magnetic exchange interactions.…”

Section: Introductionmentioning

confidence: 99%

Magnetic field driven transition from an antiferromagnetic ground state to a ferrimagnetic state in Rb0.19Ba0.3Mn1.1[Fe(CN)6]·0.48H2O Prussian blue analogue

Yusuf

Thakur

Medarde

et al. 2012

Journal of Applied Physics

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We report a magnetic field dependent (H) antiferromagnetic (AFM) to ferrimagnetic (FIM) transition in Rb 0.19 Ba 0.3 Mn 1.1 [Fe(CN) 6 ]Á0.48H 2 O Prussian blue analogue. A microscopic understanding of the nature of this field induced AFM to FIM transition is achieved by carrying out a low temperature neutron diffraction study under an external magnetic field. A decrease in N eel temperature and an evolution of a ferrimagnetic phase with an increase in dc magnetic field are evident in dc magnetic field dependent ac susceptibility measurements. With an increase in H, the FIM phase grows at the expense of the AFM phase, and for H > 4 T, the system fully transforms to the FIM phase. A magnetic structure consisting of an antiparallel stacking of ferrimagnetic sheets along crystallographic c-direction is proposed for the FIM phase. Based on the results obtained, a phase diagram describing the evolution of both magnetic phases under external magnetic field is presented. V

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“…We have studied such a compound-K 0.1 Co 4 [Fe(CN) 6 ] 2.7 ·18H 2 O, 2 with Mössbauer spectroscopy [5]. [15]. This compound exhibits ferromagnetic ordering below 10 K with a metamagnetic transition below 3 K. Mössbauer spectra of 3 ( Fig.…”

Section: Pressure Induced Electron Transfermentioning

confidence: 99%

Mössbauer spectroscopy in molecular magnetism

et al. 2009

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The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electrontransfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)-low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.

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Metal-to-metal electron transfer and magnetic interactions in a mixed-valence Prussian Blue analogue

Cited by 14 publications

References 45 publications

Enhancement of Stability by Positive Disruptive Effect on Mn–Fe Charge Transfer in Vacancy-Free Mn–Co Hexacyanoferrate Through a Charge/Discharge Process in Aqueous Na-Ion Batteries

Enhancement of Stability by Positive Disruptive Effect on Mn–Fe Charge Transfer in Vacancy-Free Mn–Co Hexacyanoferrate Through a Charge/Discharge Process in Aqueous Na-Ion Batteries

Magnetic field driven transition from an antiferromagnetic ground state to a ferrimagnetic state in Rb0.19Ba0.3Mn1.1[Fe(CN)6]·0.48H2O Prussian blue analogue

Mössbauer spectroscopy in molecular magnetism

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