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

Stock P, Deck E, Hohnstein S, Korzekwa J, Meyer K, Heinemann FW, Breher F, Hoerner G (2016)

Publication Status: Published

Publication Type: Journal article

Publication year: 2016

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 55

Pages Range: 5254-5265

Journal Issue: 11

DOI: 10.1021/acs.inorgchem.6b00238

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.

Authors with CRIS profile

Jana Korzekwa Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Karlsruhe Institute of Technology (KIT) DE Germany (DE) Technische Universität Berlin DE Germany (DE)

How to cite

APA:

Stock, P., Deck, E., Hohnstein, S., Korzekwa, J., Meyer, K., Heinemann, F.W.,... 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://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.

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