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  Time-resolved spectroscopy of photoinduced electron transfer in dinuclear and tetranuclear Fe/Co prussian blue analogues

Zimara, J., Stevens, H., Oswald, R., Demeshko, S., Dechert, S., Mata, R. A., et al. (2021). Time-resolved spectroscopy of photoinduced electron transfer in dinuclear and tetranuclear Fe/Co prussian blue analogues. Inorganic Chemistry, 60(1), 449-459. doi:10.1021/acs.inorgchem.0c03249.

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 Creators:
Zimara, J., Author
Stevens, H., Author
Oswald, R., Author
Demeshko, S., Author
Dechert, S., Author
Mata, R. A., Author
Meyer, F., Author
Schwarzer, D.1, Author           
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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Free keywords: Dynamics, experimental and computational details
 Abstract: The dynamics of the photodriven charge transfer-
induced spin transition (CTIST) in two Fe/Co Prussian Blue
Analogues (PBAs) are revealed by femtosecond IR and UV/vis
pump−probe spectroscopy. Depending on temperature, the known
tetranuclear square-type complex [Co 2 Fe 2 (CN) 6 (tp*) 2 (4,4′-
dtbbpy) 4](PF 6)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), [Fe IILS CoIIILS]2 .
Temperature rise is the reason behind thermally-induced CTIST
toward the high temperature (HT) phase consisting of low-spin
Fe(III) and high-spin Co(II), [FeIIILSCoIIHS ]2, being prevalent at
>300 K. Photoexcitation 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 [Fe IIILSCoIILS ]
intermediate which by spin-crossover (SCO) is stabilized within 400 fs to a long-lived (>1 ns) [Fe IIILSCo IIHS] species. In contrast,
IVCT excitation of the HT phase at 400 nm generates a [Fe IILSCoIIIHS] 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)]ClO 4 (2), provides a benchmark of the HT phase of 1, i.e., [Fe IIILSCo IIHS], as verified by variable
temperature magnetic susceptibility measurements and 57 Fe Mö ssbauer spectroscopy. The photoinduced charge transfer dynamics
of PBA 2 indeed are almost identical to that of the HT phase of PBA 1 with a lifetime of the excited [Fe IILSCoIIIHS ] species of 3.8 ps.

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Language(s): eng - English
 Dates: 2020-11-022020-12-172021-01-04
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.0c03249
 Degree: -

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Project name : -
Grant ID : 217133147/SFB 1073
Funding program : SFB 1073 (B06, C03)
Funding organization : DFG

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Title: Inorganic Chemistry
Source Genre: Journal
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Pages: - Volume / Issue: 60 (1) Sequence Number: - Start / End Page: 449 - 459 Identifier: ISSN: 0020-1669
ISSN: 1520-510X