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

Journal article


Publication Details

Author(s): Stock P, Deck E, Hohnstein S, Korzekwa J, Meyer K, Heinemann F, Breher F, Hoerner G
Journal: Inorganic Chemistry
Publication year: 2016
Volume: 55
Journal issue: 11
Pages range: 5254-5265
ISSN: 1520-510X


Abstract

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 (Ea ≈ 33 kJ mol(-1), from Arrhenius analysis) with stereochemical constraints. In particular, the topology of the κ(6)N ligands controls the temporary and structural dynamics during spin crossover.


FAU Authors / FAU Editors

Heinemann, Frank Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie
Korzekwa, Jana
Lehrstuhl für Anorganische und Allgemeine Chemie
Meyer, Karsten Prof. Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie


External institutions with authors

Karlsruhe Institute of Technology (KIT)
Technische Universität Berlin


How to cite

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

MLA:
Stock, Philipp, et al. "Molecular Spin Crossover in Slow Motion: Light-Induced Spin-State Transitions in Trigonal Prismatic Iron(II) Complexes." Inorganic Chemistry 55.11 (2016): 5254-5265.

BibTeX: 

Last updated on 2018-19-07 at 15:08