Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties

Research output: Contribution to journalArticleResearchpeer review

Authors

  • Michael Leibold
  • Sandra Kisslinger
  • Frank W. Heinemann
  • Frank Hampel
  • Yuko Ichiyanagi
  • Michael Klein
  • Patrick Homenya
  • Franz Renz
  • Hans Toftlund
  • Georg Brehm
  • Siegfried Schneider
  • Markus Reiher
  • Siegfried Schindler

Research Organisations

External Research Organisations

  • University of Kassel
  • Justus Liebig University Giessen
  • Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU Erlangen-Nürnberg)
  • Yokohama National University
  • University of Southern Denmark
  • ETH Zurich
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Details

Original languageEnglish
Pages (from-to)85-94
Number of pages10
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume642
Issue number1
Early online date30 Nov 2015
Publication statusPublished - 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

Cite this

Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties. / Leibold, Michael; Kisslinger, Sandra; Heinemann, Frank W. et al.
In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 642, No. 1, 01.2016, p. 85-94.

Research output: Contribution to journalArticleResearchpeer review

Leibold, M, Kisslinger, S, Heinemann, FW, Hampel, F, Ichiyanagi, Y, Klein, M, Homenya, P, Renz, F, Toftlund, H, Brehm, G, Schneider, S, Reiher, M & Schindler, S 2016, 'Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties', Zeitschrift fur Anorganische und Allgemeine Chemie, vol. 642, no. 1, pp. 85-94. https://doi.org/10.1002/zaac.201500684
Leibold, M., Kisslinger, S., Heinemann, F. W., Hampel, F., Ichiyanagi, Y., Klein, M., Homenya, P., Renz, F., Toftlund, H., Brehm, G., Schneider, S., Reiher, M., & Schindler, S. (2016). Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties. Zeitschrift fur Anorganische und Allgemeine Chemie, 642(1), 85-94. https://doi.org/10.1002/zaac.201500684
Leibold M, Kisslinger S, Heinemann FW, Hampel F, Ichiyanagi Y, Klein M et al. Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties. Zeitschrift fur Anorganische und Allgemeine Chemie. 2016 Jan;642(1):85-94. Epub 2015 Nov 30. doi: 10.1002/zaac.201500684
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title = "Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl-alkylamine Ligands on Spin Crossover Properties",
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 M{\"o}βbauer 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, M{\"o}βbauer, Spin crossover, Tetradentate pyridyl ligands",
author = "Michael Leibold and Sandra Kisslinger and Heinemann, {Frank W.} and Frank Hampel and Yuko Ichiyanagi and Michael Klein and Patrick Homenya and Franz Renz and Hans Toftlund and Georg Brehm and Siegfried Schneider and Markus Reiher and Siegfried Schindler",
note = "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 G{\"u}tlich Franz Renz ",
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Download

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

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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

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