Control of Charge-Transfer-Induced Spin Transition Temperature on Cobalt−Iron Prussian Blue Analogues

2002 ◽  
Vol 41 (4) ◽  
pp. 678-684 ◽  
Author(s):  
Naonobu Shimamoto ◽  
Shin-ichi Ohkoshi ◽  
Osamu Sato ◽  
Kazuhito Hashimoto
Keyword(s):  
Charge Transfer ◽  
Transition Temperature ◽  
Prussian Blue ◽  
Spin Transition ◽  
Prussian Blue Analogues ◽  
Cobalt Iron

scholarly journals Time-Resolved Spectroscopy of Photo-Induced Electron Transfer in Dinuclear and Tetranuclear Fe/Co Prussian Blue Analogues

2020 ◽  
Author(s):  
Jennifer Zimara ◽  
Hendrik Stevens ◽  
Rainer Oswald ◽  
Serhiy Demeshko ◽  
Sebastian Dechert ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Prussian Blue ◽  
Variable Temperature ◽  
Spin Transition ◽  
Acetonitrile Solution ◽  
Time Resolved ◽  
Thermally Induced ◽  
Prussian Blue Analogues ◽  
Charge Transfer Dynamics

The dynamics of photo-driven charge transfer-induced spin transition (CTIST) in two Fe/Co Prussian Blue Analogues (PBAs) is revealed by femtosecond IR and UV/vis pump-probe spectroscopy. Depending on temperature the known tetranuclear square-type complex [Co<sub>2</sub>Fe<sub>2</sub>(CN)<sub>6</sub>(tp*)<sub>2</sub>(4,4’-dtbbpy)<sub>4</sub>](PF<sub>6</sub>)<sub>2</sub> (<b>1</b>) exists in two electronic states. In acetonitrile solution at <240 K the low temperature (<b>LT</b>) phase is prevalent consisting of low-spin Fe(II) and low-spin Co(III), [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>LS</sub>]<sub>2</sub>. Temperature rise causes thermally induced CTIST towards the high temperature (<b>HT</b>) phase consisting of low-spin Fe(III) and high-spin Co(II), [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>]<sub>2</sub>, being prevalent at >300 K. Photo-excitation into the intervalence charge transfer (IVCT) band of the <b>LT</b> phase at 800 nm induces electron transfer in one Fe-Co edge of PBA <b>1</b> and produces a [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>LS</sub>] intermediate which by spin crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>]. In contrast, IVCT excitation of the <b>HT</b> phase at 400 nm generates a [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>HS</sub>] species with a lifetime of 3.6 ps. Subsequent back-electron transfer populates the vibrationally hot ground state, which thermalizes within 8 ps. The newly synthesized dinuclear PBA, [CoFe(CN)<sub>3</sub>(tp*)(pz*<sub>4</sub>Lut)]ClO<sub>4</sub> (<b>2</b>), provides a benchmark of the <b>HT</b> phase of <b>1</b>, i.e. [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>], as verified by variable temperature magnetic susceptibility measurements and <sup>57</sup>Fe Mößbauer spectroscopy. The photo-induced charge transfer dynamics of PBA <b>2</b> indeed is almost identical to that of the <b>HT</b> phase of phase of PBA <b>1</b> with a lifetime of the excited [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>HS</sub>] species of 3.8 ps.

Water-dependent charge-transfer-induced spin transition of Prussian blue analogues

2016 ◽  
Vol 45 (42) ◽  
pp. 16784-16788 ◽  
Author(s):  
Hitomi Ohmagari ◽  
Ryo Ohtani ◽  
Manabu Nakaya ◽  
Masaaki Ohba ◽  
Masaaki Nakamura ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Prussian Blue ◽  
Spin Transition ◽  
Coordination Geometry ◽  
Prussian Blue Analogues ◽  
Transition Behavior

Na0.46Co[Fe(CN)6]0.78(H2O)1.31 shows a water-dependent charge-transfer-induced spin transition behavior caused by a change in coordination geometry at Co centers.

scholarly journals Time-Resolved Spectroscopy of Photo-Induced Electron Transfer in Dinuclear and Tetranuclear Fe/Co Prussian Blue Analogues

2020 ◽  
Author(s):  
Jennifer Zimara ◽  
Hendrik Stevens ◽  
Rainer Oswald ◽  
Serhiy Demeshko ◽  
Sebastian Dechert ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Prussian Blue ◽  
Variable Temperature ◽  
Spin Transition ◽  
Acetonitrile Solution ◽  
Time Resolved ◽  
Thermally Induced ◽  
Prussian Blue Analogues ◽  
Charge Transfer Dynamics

The dynamics of photo-driven charge transfer-induced spin transition (CTIST) in two Fe/Co Prussian Blue Analogues (PBAs) is revealed by femtosecond IR and UV/vis pump-probe spectroscopy. Depending on temperature the known tetranuclear square-type complex [Co<sub>2</sub>Fe<sub>2</sub>(CN)<sub>6</sub>(tp*)<sub>2</sub>(4,4’-dtbbpy)<sub>4</sub>](PF<sub>6</sub>)<sub>2</sub> (<b>1</b>) exists in two electronic states. In acetonitrile solution at <240 K the low temperature (<b>LT</b>) phase is prevalent consisting of low-spin Fe(II) and low-spin Co(III), [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>LS</sub>]<sub>2</sub>. Temperature rise causes thermally induced CTIST towards the high temperature (<b>HT</b>) phase consisting of low-spin Fe(III) and high-spin Co(II), [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>]<sub>2</sub>, being prevalent at >300 K. Photo-excitation into the intervalence charge transfer (IVCT) band of the <b>LT</b> phase at 800 nm induces electron transfer in one Fe-Co edge of PBA <b>1</b> and produces a [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>LS</sub>] intermediate which by spin crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>]. In contrast, IVCT excitation of the <b>HT</b> phase at 400 nm generates a [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>HS</sub>] species with a lifetime of 3.6 ps. Subsequent back-electron transfer populates the vibrationally hot ground state, which thermalizes within 8 ps. The newly synthesized dinuclear PBA, [CoFe(CN)<sub>3</sub>(tp*)(pz*<sub>4</sub>Lut)]ClO<sub>4</sub> (<b>2</b>), provides a benchmark of the <b>HT</b> phase of <b>1</b>, i.e. [Fe<sup>III</sup><sub>LS</sub>Co<sup>II</sup><sub>HS</sub>], as verified by variable temperature magnetic susceptibility measurements and <sup>57</sup>Fe Mößbauer spectroscopy. The photo-induced charge transfer dynamics of PBA <b>2</b> indeed is almost identical to that of the <b>HT</b> phase of phase of PBA <b>1</b> with a lifetime of the excited [Fe<sup>II</sup><sub>LS</sub>Co<sup>III</sup><sub>HS</sub>] species of 3.8 ps.

scholarly journals Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

2008 ◽  
Vol 10 (38) ◽  
pp. 5882 ◽  
Author(s):  
Sébastien Bonhommeau ◽  
Niko Pontius ◽  
Saioa Cobo ◽  
Lionel Salmon ◽  
Frank M. F. de Groot ◽  
...  
Keyword(s):  
Thin Films ◽  
Charge Transfer ◽  
Prussian Blue ◽  
Absorption Spectroscopy ◽  
Metal Charge ◽  
X Ray ◽  
Prussian Blue Analogues ◽  
X Ray Absorption ◽  
Metal Charge Transfer

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

2020 ◽  
Vol 13 (1) ◽  
pp. 10-14
Author(s):  
Marco Cammarata ◽  
Serhane Zerdane ◽  
Lodovico Balducci ◽  
Giovanni Azzolina ◽  
Sandra Mazerat ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Prussian Blue ◽  
Spin Transition ◽  
Prussian Blue Analogue

Anatase-driven charge transfer involving a spin transition in cobalt iron cyanide nanostructures

2015 ◽  
Vol 17 (35) ◽  
pp. 22519-22522 ◽  
Author(s):  
Marco Giorgetti ◽  
Giuliana Aquilanti ◽  
Michela Ciabocco ◽  
Mario Berrettoni
Keyword(s):  
Charge Transfer ◽  
Spin Transition ◽  
Iron Cyanide ◽  
Cobalt Hexacyanoferrate ◽  
Cobalt Iron ◽  
A Charge

A charge transfer between Fe and Co in cobalt hexacyanoferrate takes place with concomitant spin transition at the Co site.

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