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Weber, Birgit ; Bauer, Wolfgang ; Pfaffeneder, Toni ; Dîrtu, Marinela M. ; Naik, Anil D. ; Rotaru, Aurelian ; Garcia, Yann:
Influence of Hydrogen Bonding on the Hysteresis Width in Iron(II) Spin-Crossover Complexes.
In: European Journal of Inorganic Chemistry.
Bd. 2011
(2011)
Heft 21
.
- S. 3193-3206.
ISSN 1099-0682
DOI: https://doi.org/10.1002/ejic.201100394
Abstract
A detailed investigation on the properties of the high-temperature and low-temperature modifications of the iron(II) spin-crossover complex [FeL1(HIm)2] (1) and its isotopic deuterium-labelled analogue [FeL1(DIm)2] (1D), and the pair [FeL2(azpy)]·MeOH/[FeL2(azpy)]·CD3OD/[FeL2(azpy)] (2·MeOH/2·CD3OD/2), in which L1 and L2 are tetradentate N2O22–-coordinating Schiff base like ligands, L1 = {diethyl(E,E)-2,2′-[1,2-phenylbis(iminomethylidyne)]bis[3-oxobutanoate](2–)-N,N′,O3,O3′}, L2 = {2,2′-[1,2-phenylbis(iminomethylidyne)]bis[1-phenylbutane-1,3-dione](2–)-N,N′,O3,O3′},HIm = imidazole, and azpy = 4,4′-azopyridine, is presented. All complexes except 2 show a cooperative spin transition with hysteresis widths between approximately 5 K (1LT and 1LTD), 70 K (1HT[9] and 1HTD, around room temperature), and 80 K (2·MeOH and 2·CD3OD). In all cases, an influence of the H/D exchange on the transition temperature and the hysteresis width is observed. For 1HT, first-order reversal curves (FORCs) have been recorded, and a statistical analysis gives the interaction parameter J = 560 K, indicating strong intermolecular interactions. X-ray structural analysis of the different samples (1HT[9] and 1HTD: HS; 1LT and 1LTD: LS; and 2·MeOH and 2·CD3OD: HS) gives a deeper insight into the molecular packing in the crystals and helps explain the increase of cooperative interactions during the spin transition. In all cases, one hydrogen bond involves an oxygen atom of the Schiff base like ligand that serves as a donor for the iron centre. The influence of this hydrogen bond on the ligand field strength of the iron centre is discussed and a new model is developed to explain the observed connection between hydrogen bonds and exceptionally wide hysteresis loops for the complexes presented in this work and other examples from the literature.
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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 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: | 27 Jul 2017 12:09 |
| Letzte Änderung: | 27 Jul 2017 12:09 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/38836 |