Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue

Cammarata, Marco; Zerdane, Serhane; Balducci, Lodovico; Azzolina, Giovanni; Mazérat, Sandra; Exertier, Cécile; Trabuco, Matilde Cardoso; Levantino, Matteo; Alonso-Mori, Roberto; Glownia, James M.; Song, Sanghoon; Catala, Laure; Mallah, Talal; Matar, Samir F.; Collet, Éric

doi:10.1038/s41557-020-00597-8

Cited by 132 publications

(152 citation statements)

References 35 publications

(66 reference statements)

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“…The net reaction is water splitting with undistinguished production of H 2 and O 2 at nanoscale interface in the open system, which also answers the origin of bimetal NPs catalyzed water splitting. But, the experimental phenomenon of anti-galvanic replacement is completely right ( Jeon et al, 2013 ; Jiao et al, 2019 ; Cammarata et al, 2021 ). Indeed, our proposed model of SWs as emitters with transient states benefiting electron transfer provides a reliable explanation of why the Ag NCs or NPs are very easy to be oxidized under air atmosphere.…”

Section: Resultsmentioning

confidence: 99%

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

et al. 2021

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On the origin of photoluminescence of noble metal NCs, there are always hot debates: metal-centered quantum-size confinement effect VS ligand-centered surface state mechanism. Herein, we provided solid evidence that structural water molecules (SWs) confined in the nanocavity formed by surface-protective-ligand packing on the metal NCs are the real luminescent emitters of Au-Ag bimetal NCs. The Ag cation mediated Au-Ag bimetal NCs exhibit the unique pH-dependent dual-emission characteristic with larger Stokes shift up to 200 nm, which could be used as potential ratiometric nanosensors for pH detection. Our results provide a completely new insight on the understanding of the origin of photoluminescence of metal NCs, which elucidates the abnormal PL emission phenomena, including solvent effect, pH-dependent behavior, surface ligand effect, multiple emitter centers, and large-Stoke’s shift.

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Section: Resultsmentioning

confidence: 99%

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

et al. 2021

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“…Combined powder X-ray diffraction, magnetic, Electron Paramagnetic Resonance, and X-ray photoelectron spectroscopy studies are consistent with the presence at room temperature of the different phases Co II Fe II , Co II Fe III , and Co III Fe II , the latter contributing to 70% of the overall concentration of each nanocrystal [8]. Because of their stability as isolated objects in water, they were used to unravel the mechanisms of charge transfer and spin crossover after light irradiation [10]. They were also deposited on graphite and their conductance was measured, showing a long range electron transport with relatively weak attenuation [11].…”

Section: Methodsmentioning

confidence: 70%

Collective Magnetic Behavior of 11 nm Photo-Switchable CsCoFe Prussian Blue Analogue Nanocrystals: Effect of Dilution and Light Intensity

Trinh¹,

Rivière²,

Mazérat³

et al. 2021

Magnetochemistry

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The collective magnetic behavior of photoswitchable 11 nm cyanide-bridged nanoparticles based of the Prussian blue analogue CsCoFe were investigated when embedded in two different matrices with different concentrations. The effect of the intensity of light irradiation was studied in the less concentrated sample. Magnetization studies and alternating magnetic susceptibility data are consistent with a collective magnetic behavior due to interparticle dipolar magnetic interaction for the two compounds, even though the objects have a size that place them in the superparamagnetic regime.

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“…33 Later, Glatz decorated a partly reduced cube with the Cs@{Fe II,LS 4 -Fe III,HS 3 Fe II,HS } core, in which the only high-spin Fe(II) center exhibited SCO behaviour. 34 Different from the normally observed charge-transfer induced spin transition (CTIST) in the heterometallic Fe/Co compounds, 35,36 the CT and spin transition (ST) processes may proceed more separately in the Fe-Fe system, whereas more efforts are needed to figure out how it works. [41][42][43]…”

Section: Introductionmentioning

confidence: 95%

Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence {Fe ^III ₄ Fe ^II ₄ } Cubes

et al. 2022

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The engineering of switchable molecules with dramatic magnetic change is currently among the most active research area. Here, two cyanide-bridged mixed-valence {Fe III 4 Fe II 4 } cubes were prepared, interestingly, both of which exhibited reversible thermally-induced metal-to-metal charge transfer (MMCT) behavior between {Fe III,LS 4 Fe II,HS 4 } and {Fe II,LS 4 Fe III,HS 4 } configurations with the transition temperature (T 1/2 ) of 274 and 230 K, respectively, establishing a rare example of discrete homometallic complexes showing the reversible MMCT rather than spin crossover behaviour. In stark contrast to the heterometallic Fe/Co system, in which the CT and spin transition (ST) processes occur simultaneously, the detailed structural and Mössbauer spectroscopy analysis confirmed the solely CT property without spin transition involved for the current case. In addition, both of them showed excellent redox flexibility in solution with seven quasi accessible electronic states.

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Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue

Cited by 132 publications

References 35 publications

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

Collective Magnetic Behavior of 11 nm Photo-Switchable CsCoFe Prussian Blue Analogue Nanocrystals: Effect of Dilution and Light Intensity

Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence {Fe ^III ₄ Fe ^II ₄ } Cubes

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Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue

Cited by 132 publications

References 35 publications

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

Physical Origin of Dual-Emission of Au–Ag Bimetallic Nanoclusters

Collective Magnetic Behavior of 11 nm Photo-Switchable CsCoFe Prussian Blue Analogue Nanocrystals: Effect of Dilution and Light Intensity

Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence {Fe III 4 Fe II 4 } Cubes

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Thermally Induced Reversible Metal-to-Metal Charge Transfer in Mixed-Valence {Fe ^III ₄ Fe ^II ₄ } Cubes