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

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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. Bd. 55 (2016) Heft 11 . - S. 5254-5265.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.6b00238

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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.