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Structural Aspects of Spin Crossover. Example of the [FeIILn(NCS)2] Complexes

  • Chapter
Spin Crossover in Transition Metal Compounds II

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

Abstract

The interplay between the spin crossover and the structural properties of the complexes in the solid state is still under investigation. In particular the following questions may be asked. What are the structural modifications of the metal coordination sphere at the spin crossover? How are the dimensions and the symmetry of the crystallographic unit cell affected by the spin crossover? Conversely, how may structural properties influence the spin crossover behavior? Do intramolecular parameters account for the features of the spin crossover? What are the relevant characteristics of the crystal packing for the cooperativity? Do the above questions have general answers that can be used for all the spin crossover compounds? This contribution tries to give answers to these questions. The discussion is based on a large structural data set provided in the literature for the six-coordinated iron(II) mononuclear complexes of general formula [FeLn(NCS)2]. The effects of temperature, light and pressure on the X-ray diffraction crystal structures are reviewed. The structural modifications due to the spin crossover are first estimated, these include the expansion and the distortion of the FeN6 octahedron, the isotropic and the anisotropic changes of the unit cell. The influence of the structural properties on the features of the spin crossover is then discussed. For example, intramolecular properties such as Fe-N bond lengths are in general not relevant to account for the spin crossover features. In contrast, hydrogen bonds play a paramount role in the propagation of the spin conversion throughout the crystal lattice.

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Abbreviations

abpt:

4-Amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole

AzA:

4-(Phenylazo)aniline

BiA:

4-(Aminobiphenyl)aniline

bpy:

2,2′-Bipyridine

bpym:

2,2′-Bipyrimidine

bt:

2,2′-Bi-2-thiazoline

btz:

2,2′-Bi-4,4-dihydrothiazine

DiyA:

4-(Phenylbutadiyne)aniline

dmp:

2,9-Dimethyl-1,10-phenanthroline

dpea:

(2-Aminoethyl)bis(2-pyridylmethyl)amine

dpp:

Dipyrido[3,2-a:2′,3′-c]phenazine

dppa:

(3-Aminopropyl)bis(2-pyridyl-methyl)amine

dpq:

2,3-Bis-(2′-pyridyl)-quinoxaline

HS:

High spin

LS:

Low spin

LIESST:

Light-Induced Excited Spin-State Trapping

mtz:

Methyltetrazole

PeA:

4-(Phenylethynyl)aniline

phen:

1,10-Phenanthroline

PM:

N-(2′-Pyridylmethylene)

pic:

Picolylamine (2-aminomethyl-pyridine)

ptz:

1-Propyltetrazole

py:

Pyridine

tap:

1,4,5,8-Tetraazaphenanthrene

SCO:

Spin crossover

stpy:

4-Styrylpyridine

tap:

Bis(1,4,5,8-tetraazaphenanthrene)

TeA:

4-(Aminoterphenyl)aniline

TheA:

4-(Thienylethynyl)aniline

TIA:

N-o-Tolyl-2-imidazolaldimine

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Acknowledgment

The authors thank the European community for supporting our research through the TMR network TOSS ERB-FMRX-CT98-0199.

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Authors and Affiliations

  1. Institut de Chimie de la Matière Condensée de Bordeaux, UPR CNRS 9048, Université Bordeaux I, 87 Av. Dr A. Schweitzer, 33608, Pessac, France

    Philippe Guionneau, Mathieu Marchivie, Georges Bravic, Jean-François Létard & Daniel Chasseau

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  1. Philippe Guionneau
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  2. Mathieu Marchivie
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Correspondence to Philippe Guionneau .

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Guionneau, P., Marchivie, M., Bravic, G., Létard, JF., Chasseau, D. Structural Aspects of Spin Crossover. Example of the [FeIILn(NCS)2] Complexes. In: Spin Crossover in Transition Metal Compounds II. Topics in Current Chemistry, vol 234. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b95414

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  • DOI: https://doi.org/10.1007/b95414

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-40396-8

  • Online ISBN: 978-3-540-36774-1

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