Details
| Original language | English |
|---|---|
| Pages (from-to) | 85-94 |
| Number of pages | 10 |
| Journal | Zeitschrift fur Anorganische und Allgemeine Chemie |
| Volume | 642 |
| Issue number | 1 |
| Early online date | 30 Nov 2015 |
| Publication status | Published - Jan 2016 |
Abstract
Iron(II) complexes of the type [Fe(L)(NCS)2] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)2] [tmpa = tris(2-pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)2], [Fe(pmap)(NCS)2], and [Fe(tepa)(NCS)2] [pmea = N,N-bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine, pmap = N,N-bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine, and tepa = tris[2-(2-pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Möβbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl-alkylamine ligands is clearly demonstrated.
Keywords
- Iron, LIESST effect, Möβbauer, Spin crossover, Tetradentate pyridyl ligands
ASJC Scopus subject areas
- Chemistry(all)
- Inorganic Chemistry
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In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 642, No. 1, 01.2016, p. 85-94.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties
AU - Leibold, Michael
AU - Kisslinger, Sandra
AU - Heinemann, Frank W.
AU - Hampel, Frank
AU - Ichiyanagi, Yuko
AU - Klein, Michael
AU - Homenya, Patrick
AU - Renz, Franz
AU - Toftlund, Hans
AU - Brehm, Georg
AU - Schneider, Siegfried
AU - Reiher, Markus
AU - Schindler, Siegfried
N1 - Funding Information: and (DFG Re‐1627) gratefully acknowledge the Deutsche Forschungsgemeinschaft and for support of this work. thanks the Deutscher Akademischer Austauschdienst and the Leibniz University Hannover (ZFM and LNQE) Siegfried Schindler Franz Renz Philipp Gütlich Franz Renz
PY - 2016/1
Y1 - 2016/1
N2 - Iron(II) complexes of the type [Fe(L)(NCS)2] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)2] [tmpa = tris(2-pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)2], [Fe(pmap)(NCS)2], and [Fe(tepa)(NCS)2] [pmea = N,N-bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine, pmap = N,N-bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine, and tepa = tris[2-(2-pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Möβbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl-alkylamine ligands is clearly demonstrated.
AB - Iron(II) complexes of the type [Fe(L)(NCS)2] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)2] [tmpa = tris(2-pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)2], [Fe(pmap)(NCS)2], and [Fe(tepa)(NCS)2] [pmea = N,N-bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine, pmap = N,N-bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine, and tepa = tris[2-(2-pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Möβbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl-alkylamine ligands is clearly demonstrated.
KW - Iron
KW - LIESST effect
KW - Möβbauer
KW - Spin crossover
KW - Tetradentate pyridyl ligands
UR - http://www.scopus.com/inward/record.url?scp=84954178331&partnerID=8YFLogxK
U2 - 10.1002/zaac.201500684
DO - 10.1002/zaac.201500684
M3 - Article
AN - SCOPUS:84954178331
VL - 642
SP - 85
EP - 94
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
SN - 0044-2313
IS - 1
ER -