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Synthesis and Characterisation of Two New Iron(II) Spin-Crossover Complexes with N₄O₂ Coordination Spheres : Optimizing Preconditions for Cooperative Interactions

Titelangaben

Weber, Birgit ; Kaps, Eike ; Desplanches, Cédric ; Létard, Jean-François ; Achterhold, Klaus ; Parak, Fritz G.:
Synthesis and Characterisation of Two New Iron(II) Spin-Crossover Complexes with N₄O₂ Coordination Spheres : Optimizing Preconditions for Cooperative Interactions.
In: European Journal of Inorganic Chemistry. Bd. 2008 (2008) Heft 31 . - S. 4891-4898.
ISSN 1099-0682
DOI: https://doi.org/10.1002/ejic.200800420

Abstract

Two new spin-crossover complexes, [FeL1(phpy)2] (1) and [FeL2(phpy)2](phpy) (2), with L1 and L2 being tetradentate N2O22–-coordinating Schiff-base-like ligands {L1 = (E,E)-[diethyl 2,2′-[1,2-phenylenebis(iminomethylidyne)]bis(3-oxobutanoato)(2–)-N,N′,O3,O3′], L2 = [(3,3′)-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2–)-N,N′,O2,O2′]and phpy = 4-phenylpyridine} have been investigated using temperature-dependent susceptibility and photomagnetic measurements, as well as Mössbauer spectroscopy and X-ray structure analysis. Compound 1 shows a cooperative spin transition with a thermal hysteresis loop approximately 4 K wide (T1/2↓ = 232 K and T1/2↑ = 236 K). The spin transition of 2 is gradual with T1/2 ≈ 290 K. Results from X-ray structure analysis indicate that the cooperative interactions are due to elastic interactions with several intense C–C contacts in the case of 1. The change of the spin state at the iron centre is accompanied by a change of the O–Fe–O angle, the so-called bite of the equatorial ligand, from 107° in the high-spin state to 89° in the low-spin state. Reflectivity measurements of 1 indicate that the Light-Induced Excited Spin State Trapping (LIESST) effect occurs at the sample surface at low temperatures. In the bulk solid, photomagnetic properties with a photoexcitation level of 30 % and a T(LIESST) value of 41 K are observed using a SQUID magnetometer.

Weitere Angaben

Publikationsform: Artikel in einer Zeitschrift
Begutachteter Beitrag: Ja
Institutionen der Universität: Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie IV > Professur Anorganische Chemie IV - Univ.-Prof. Dr. Birgit Weber
Fakultäten
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie IV
Titel an der UBT entstanden: Nein
Themengebiete aus DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Eingestellt am: 28 Jul 2017 09:09
Letzte Änderung: 28 Jul 2017 09:09
URI: https://eref.uni-bayreuth.de/id/eprint/38856