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Structural Investigations of Tetrazole Complexes of Iron(II)

  • Chapter
Spin Crossover in Transition Metal Compounds II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 234))

Abstract

The results of X-ray diffraction studies of spin crossover complexes of iron(II) with R=1-propyl- (ptz), 1- methyl- (mtz) and 1-ethyltetrazole (etz) ligands, [Fe(Rtz)6](BF4)2, as a function of temperature (down to 10 K) and after light-induced conversion to long-lived metastable spin states (LIESST) are reviewed. Not only has the most prominent member of this class of spin crossover compounds, viz. [Fe(ptz)6](BF4)2, been studied very extensively, particularly in relation to its photophysical properties and cooperative interactions in solids, but this general class of spin crossover complexes has also attracted much interest from a crystallographic point of view. [Fe(ptz)6](BF4)2 has only one type of lattice site for the iron(II) centres, but it is possible to generate five different phases depending on the rate of cooling the sample on the one hand and on irradiation with light on the other. The methyl and ethyl-tetrazole derivatives, also being mononuclear systems, show the peculiarity that the iron(II) ions occupy two different lattice sites (A and B), with ratio 1:1 in the mtz complex and 2:1 in the etz complex, where only A site ions undergo thermal spin transition but B site ions remain in the high spin state at all temperatures under study. The LIESST phenomenon has been verified at A and B lattice sites generating metastable HS states at A sites with green light and metastable LS states at B sites. Three possible phases created this way in the case of the mtz complex have been structurally characterised.

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Abbreviations

SCO:

Spin crossover

HS:

High spin

LS:

Low spin

γHS :

Molar fraction of HS molecules

LIESST:

Light induced excited spin state trapping

T1/2 :

Spin transition temperature (temperature of 50% conversion of all SCO-active complex molecules)

mtz:

1-Methyl-tetrazole

etz:

1-Ethyl-tetrazole

ptz:

1-n-Propyl-tetrazole

pic:

2-Picolylamine

phen:

1,10-Phenanthroline

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Acknowledgements

We are grateful for financial support from the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, the European Community (TMR Network No. ERB-FMRX-CT98-0199, “Thermal and Optical Switching of Molecular Spin States”, TOSS) and the Materialwissenschaftliches Forschungszentrum der Universität Mainz.

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Author notes

  1. Joachim Kusz

    Present address: Institute of Physics, University of Silesia, Katowice, Poland

Authors and Affiliations

  1. Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg-Universität Mainz, Mainz, Germany

    Joachim Kusz, Philipp Gütlich & Hartmunt Spiering

Authors
  1. Joachim Kusz
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  2. Philipp Gütlich
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  3. Hartmunt Spiering
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Correspondence to Joachim Kusz or Philipp Gütlich .

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Dedicated to Professor Hans Bock on the occasion of his 75th birthday.

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Kusz, J., Gütlich, P., Spiering, H. Structural Investigations of Tetrazole Complexes of Iron(II). In: Spin Crossover in Transition Metal Compounds II. Topics in Current Chemistry, vol 234. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b95415

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  • DOI: https://doi.org/10.1007/b95415

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-40396-8

  • Online ISBN: 978-3-540-36774-1

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