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  Molecular Spin Crossover in Slow Motion: Light-Induced Spin-State Transitions in Trigonal Prismatic Iron(II) Complexes

Stock, P., Deck, E. P., Hohnstein, S., Korzekwa, J., Meyer, K., Heinemann, F. W., et al. (2016). Molecular Spin Crossover in Slow Motion: Light-Induced Spin-State Transitions in Trigonal Prismatic Iron(II) Complexes. Inorganic Chemistry, 55(11), 5254-5265. doi:10.1021/acs.inorgchem.6b00238.

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 Creators:
Stock, Philipp1, 2, Author           
Deck, Eva P.3, Author           
Hohnstein, Silvia3, Author           
Korzekwa, Jana4, Author           
Meyer, Karsten4, Author           
Heinemann, Frank W.4, Author           
Breher, Frank3, Author           
Hörner, Gerald5, Author           
Affiliations:
1Institut für Chemie, Technische Universität Berlin, Berlin, Germany, ou_persistent22              
2Interaction Forces and Functional Materials, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society, ou_1863357              
3Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, Karlsruhe, Germany, persistent22              
4Department Chemie und Pharmazie, Anorganische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 1, Erlangen, Germany, persistent22              
5Institut für Chemie, Sekr. C2, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany, ou_persistent22              

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 Abstract: A straightforward access is provided to iron(II) complexes showing exceedingly slow spin-state interconversion by utilizing trigonal-prismatic directing ligands (Ln) of the extended-tripod type. A detailed analysis of the interrelations between complex structure (X-ray diffraction, density functional theory) and electronic character (SQUID magnetometry, Mössbauer spectroscopy, UV/vis spectroscopy) of the iron(II) center in mononuclear complexes [FeLn] reveals spin crossover to occur along a coupled breathing/torsion reaction coordinate, shuttling the complex between the octahedral low-spin state and the trigonal-prismatic high-spin state along Bailar's trigonal twist pathway. We associate both the long spin-state lifetimes in the millisecond domain close to room temperature and the substantial barriers against thermal scrambling (Ea ≈ 33 kJ mol-1, from Arrhenius analysis) with stereochemical constraints. In particular, the topology of the κ6N ligands controls the temporary and structural dynamics during spin crossover. © 2016 American Chemical Society.

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Language(s): eng - English
 Dates: 2016-06-06
 Publication Status: Issued
 Pages: -
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.6b00238
BibTex Citekey: Stock20165254
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 55 (11) Sequence Number: - Start / End Page: 5254 - 5265 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669