Details

Autor(en) / Beteiligte

• Stock, Philipp
• Deck, Eva
• Hohnstein, Silvia
• Korzekwa, Jana
• Meyer, Karsten
• Heinemann, Frank W
• Breher, Frank
• Hörner, Gerald

Titel

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

Ist Teil von

• Inorganic chemistry, 2016-06, Vol.55 (11), p.5254-5265

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2016

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• A straightforward access is provided to iron­(II) complexes showing exceedingly slow spin-state interconversion by utilizing trigonal-prismatic directing ligands (L n ) 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 [FeL n ] 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 (E a ≈ 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.