Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues CIxCo4[Fe(CN)6]y(CI= Alkali Cation). 3. Control of the Photo- and Thermally Induced Electron Transfer by the [Fe(CN)6] Vacancies in Cesium Derivatives

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 [Co2Fe2(CN)6(tp*)2(4,4’-dtbbpy)4](PF6)2 (1) exists in two electronic states. In acetonitrile solution at <240 K the low temperature (LT) phase is prevalent consisting of low-spin Fe(II) and low-spin Co(III), [FeIILSCoIIILS]2. Temperature rise causes thermally induced CTIST towards the high temperature (HT) phase consisting of low-spin Fe(III) and high-spin Co(II), [FeIIILSCoIIHS]2, being prevalent at >300 K. Photo-excitation into the intervalence charge transfer (IVCT) band of the LT phase at 800 nm induces electron transfer in one Fe-Co edge of PBA 1 and produces a [FeIIILSCoIILS] intermediate which by spin crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [FeIIILSCoIIHS]. In contrast, IVCT excitation of the HT phase at 400 nm generates a [FeIILSCoIIIHS] 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)3(tp*)(pz*4Lut)]ClO4 (2), provides a benchmark of the HT phase of 1, i.e. [FeIIILSCoIIHS], as verified by variable temperature magnetic susceptibility measurements and 57Fe Mößbauer spectroscopy. The photo-induced charge transfer dynamics of PBA 2 indeed is almost identical to that of the HT phase of phase of PBA 1 with a lifetime of the excited [FeIILSCoIIIHS] species of 3.8 ps.

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

10.26434/chemrxiv.13169198 ◽

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 [Co2Fe2(CN)6(tp*)2(4,4’-dtbbpy)4](PF6)2 (1) exists in two electronic states. In acetonitrile solution at <240 K the low temperature (LT) phase is prevalent consisting of low-spin Fe(II) and low-spin Co(III), [FeIILSCoIIILS]2. Temperature rise causes thermally induced CTIST towards the high temperature (HT) phase consisting of low-spin Fe(III) and high-spin Co(II), [FeIIILSCoIIHS]2, being prevalent at >300 K. Photo-excitation into the intervalence charge transfer (IVCT) band of the LT phase at 800 nm induces electron transfer in one Fe-Co edge of PBA 1 and produces a [FeIIILSCoIILS] intermediate which by spin crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [FeIIILSCoIIHS]. In contrast, IVCT excitation of the HT phase at 400 nm generates a [FeIILSCoIIIHS] 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)3(tp*)(pz*4Lut)]ClO4 (2), provides a benchmark of the HT phase of 1, i.e. [FeIIILSCoIIHS], as verified by variable temperature magnetic susceptibility measurements and 57Fe Mößbauer spectroscopy. The photo-induced charge transfer dynamics of PBA 2 indeed is almost identical to that of the HT phase of phase of PBA 1 with a lifetime of the excited [FeIILSCoIIIHS] species of 3.8 ps.

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Photo-induced electron transfer in ferrimagnetic Prussian-blue analogues XIxCo4[Fe(CN)6]y (XI = alkali cation)

Comptes Rendus Chimie ◽

10.1016/j.crci.2003.06.006 ◽

2003 ◽

Vol 6 (8-10) ◽

pp. 1165-1173 ◽

Cited By ~ 6

Author(s):

Virginie Escax ◽

Christophe Cartier dit Moulin ◽

Françoise Villain ◽

Guillaume Champion ◽

Jean-Paul Itié ◽

...

Keyword(s):

Electron Transfer ◽

Prussian Blue ◽

Alkali Cation ◽

Prussian Blue Analogues ◽

Photo Induced Electron Transfer

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Thermally Induced Electron Transfer in a CsCoFe Prussian Blue Derivative: The Specific Role of the Alkali-Metal Ion

Angewandte Chemie ◽

10.1002/ange.200460086 ◽

2004 ◽

Vol 116 (28) ◽

pp. 3814-3817 ◽

Cited By ~ 17

Author(s):

Anne Bleuzen ◽

Virginie Escax ◽

Alban Ferrier ◽

Françoise Villain ◽

Michel Verdaguer ◽

...

Keyword(s):

Electron Transfer ◽

Alkali Metal ◽

Prussian Blue ◽

Metal Ion ◽

Specific Role ◽

Alkali Metal Ion ◽

Thermally Induced

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Thermally Induced Dilution of the Photo-Induced Magnetic State of Prussian Blue Analogues

Molecular Crystals and Liquid Crystals ◽

10.1080/713738677 ◽

2002 ◽

Vol 379 (1) ◽

pp. 333-340 ◽

Cited By ~ 24

Author(s):

F. Varret ◽

A. Goujon ◽

K. Boukheddaden ◽

M. NoguÈS ◽

A. Bleuzen ◽

...

Keyword(s):

Prussian Blue ◽

Magnetic State ◽

Thermally Induced ◽

Prussian Blue Analogues

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Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues CIxCo4[Fe(CN)6]y(CI= Alkali Cation). 1. Conditions to Observe the Phenomenon

Journal of the American Chemical Society ◽

10.1021/ja000348u ◽

2000 ◽

Vol 122 (28) ◽

pp. 6648-6652 ◽

Cited By ~ 338

Author(s):

Anne Bleuzen ◽

Claire Lomenech ◽

Virginie Escax ◽

Françoise Villain ◽

François Varret ◽

...

Keyword(s):

Prussian Blue ◽

Alkali Cation ◽

Prussian Blue Analogues

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Time-Resolved Spectroscopy of Photoinduced Electron Transfer in Dinuclear and Tetranuclear Fe/Co Prussian Blue Analogues

Inorganic Chemistry ◽

10.1021/acs.inorgchem.0c03249 ◽

2020 ◽

Vol 60 (1) ◽

pp. 449-459

Author(s):

Jennifer Zimara ◽

Hendrik Stevens ◽

Rainer Oswald ◽

Serhiy Demeshko ◽

Sebastian Dechert ◽

...

Keyword(s):

Electron Transfer ◽

Prussian Blue ◽

Photoinduced Electron Transfer ◽

Time Resolved ◽

Time Resolved Spectroscopy ◽

Prussian Blue Analogues

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Photomagnetic CoFe Prussian Blue Analogues: Role of the Cyanide Ions as Active Electron Transfer Bridges Modulated by Cyanide−Alkali Metal Ion Interactions

Journal of the American Chemical Society ◽

10.1021/ja102660b ◽

2010 ◽

Vol 132 (33) ◽

pp. 11552-11559 ◽

Cited By ~ 57

Author(s):

Jean-Daniel Cafun ◽

Guillaume Champion ◽

Marie-Anne Arrio ◽

Christophe Cartier dit Moulin ◽

Anne Bleuzen

Keyword(s):

Electron Transfer ◽

Alkali Metal ◽

Prussian Blue ◽

Metal Ion ◽

Alkali Metal Ion ◽

Prussian Blue Analogues ◽

Ion Interactions ◽

Active Electron ◽

Metal Ion Interactions

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Alkali Cation Potential and Functionality in the Nanoporous Prussian Blue Analogues

Advances in Condensed Matter Physics ◽

10.1155/2013/539620 ◽

2013 ◽

Vol 2013 ◽

pp. 1-9 ◽

Cited By ~ 7

Author(s):

Yutaka Moritomo ◽

Hiroshi Tanaka

Keyword(s):

Prussian Blue ◽

Lithium Ion ◽

Nanoporous Materials ◽

Alkali Cation ◽

Energy Calculation ◽

Molecular Sensors ◽

Prussian Blue Analogues ◽

Total Energy Calculation ◽

Secondary Battery ◽

Potential Curves

Cation and/or molecule transfer within nanoporous materials is utilized in lithium-ion secondary battery, ion exchange, hydrogen storage, molecular sensors, molecular filters, and so on. Here, we performedab initiototal energy calculation to derive the alkali cation potential in the Prussian blue analogues,AxM[Fe(CN)6]zH2O(A=Li, Na, K, Rb, and Cs;M=Co, Ni, Mn, and Cd), with jungle-gym-type nanoporous framework. The potential curves of larger cations, that is, K+, Rb+and Cs+, exhibit a barrier at the window of the host framework, while those of the smaller cations, that is, Li+and Na+, exhibit no barrier. We will discuss the useful functionalities observed in the Prussian blue analogues, that is, (a) battery properties mediated by Li+intercalation/de-intercalation, (b) electrochromism mediated by Na+transfer in all solid device, and (c) the elimination of Cs+from aqueous solution by precipitation, in terms of the alkali cation potentials.

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