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Kinetic Trapping Effects in Amphiphilic Iron(II) Spin Crossover Compounds


Weihermüller, Johannes ; Schlamp, Stephan ; Dittrich, Birger ; Weber, Birgit:
Kinetic Trapping Effects in Amphiphilic Iron(II) Spin Crossover Compounds.
In: Inorganic Chemistry. Bd. 58 (2019) Heft 2 . - S. 1278-1289.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.8b02763


In this work, the synthesis of four new iron complexes with a Schiff base-like amphiphilic equatorial ligand (L) and dimethylaminopyridine (dmap) or 4,4′-bipyridine (bipy) as axial ligands is reported. Three of the complexes ([FeL(dmap)2] 1, [FeL(dmap)(MeOH)0.5]·MeOH 2, and [FeL(bipy)]n 3 have an iron(II) center, and two of those with an N4O2 coordination sphere (1 and 3) are spin crossover active. Both exhibit a thermal hysteresis (10 K with T1/2 = 131 K for 3 and 23 K with T1/2 = 161 K for 1) where the width depends on the velocity used for the measurement. Additionally, in both cases, the high spin state is trapped by rapid cooling, and a TTIESST was determined to be 121 K (1) and 101 K (3). Single crystals suitable for X-ray structure analysis were obtained for the three different complexes with dmap as axial ligand (1S, 2, and [μ-O-{FeL}2(dmap)] 4). The complex 1S has two dmap molecules in axial position, while the other two structures were obtained for a complex where a dmap ligand is exchanged by methanol and one where the iron(II) center is oxidized to iron(III) to form a dinuclear μ-O-complex. All three complexes were obtained under similar reaction conditions in the presence/absence of oxygen, and all three structures show the formation of lipid layer-like arrangements in the packing.

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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
Titel an der UBT entstanden: Ja
Themengebiete aus DDC: 500 Naturwissenschaften und Mathematik > 540 Chemie
Eingestellt am: 04 Feb 2019 08:49
Letzte Änderung: 04 Feb 2019 08:49
URI: https://eref.uni-bayreuth.de/id/eprint/47161