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

Title data

Stock, Philipp ; Deck, Eva ; Hohnstein, Silvia ; Korzekwa, Jana ; Meyer, Karsten ; Heinemann, Frank W. ; Breher, Frank ; Hörner, Gerald:
Molecular Spin Crossover in Slow Motion : Light-Induced Spin-State Transitions in Trigonal Prismatic Iron(II) Complexes.
In: Inorganic Chemistry. Vol. 55 (9 May 2016) Issue 11 . - pp. 5254-5265.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.6b00238

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

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.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Result of work at the UBT: No
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 06 Jul 2020 12:41
Last Modified: 06 Jul 2020 12:41
URI: https://eref.uni-bayreuth.de/id/eprint/55711