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Spin Crossover in Transition Metal Compounds III pp 23–64Cite as

Pressure Effect Studies on Spin Crossover and Valence Tautomeric Systems

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 235))

Abstract

In the present review chapter we discuss the results of investigations of the influence of hydrostatic pressure (up to 1.2 GPa) on the spin transition behaviour in coordination compounds of 3d transition metal ions. The systems under investigation are mononuclear spin crossover compounds of iron(II) and chromium(II), dinuclear complexes of iron(II) exhibiting coexistence of intramolecular antiferromagnetic coupling and thermal spin crossover, and 1D, 2D and 3D polynuclear spin crossover complexes of iron(II). Results from studies of the effect of pressure on coordination compounds exhibiting thermally induced electron transfer with subsequent spin state changes are also presented and discussed. It is demonstrated that pressure effect studies are very helpful in elucidating the mechanism of cooperative dynamic electronic structure phenomena accompanied by significant volume changes. Application of hydrostatic pressure serves as a tool for modifying the ligand field strength in a controlled manner.

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Abbreviations

ST:

Spin transition

SCO:

Spin crossover

HS:

High spin

LS:

Low spin

χM :

Molar magnetic susceptibility

T 1/2 :

Temperature at which 50% of the “ST-active” molecules change the spin state

T c :

Critical temperature of spin transition

ΔT 1/2 :

Hysteresis width of spin transition

P:

Pressure

P1/2 :

Pressure at which 50% of the “ST-active” molecules change the spin state

Pc :

Critical pressure of spin transition

γHS :

HS molar fraction

γHS(T):

HS molar fraction as a function of temperature

γLS :

LS molar fraction

γG :

Grüneisen parameter

γ0 :

Eshelby constant

H:

Magnetic field

ZFS:

Zero field splitting

ΔS:

Entropy difference between the HS and LS states

ΔH:

Enthalpy difference between the HS and LS states

Γ:

Parameter accounting for intermolecular interactions

K:

Bulk modulus

V:

Volume

ΔV:

Molecular volume change between HS and LS species

fint(γ, T):

Free energy of intermolecular interaction

G:

Gibbs free energy

ΔF HL :

Change of the (Helmholtz) free energy due to spin transition

Δ s :

Energy shift of the lattice upon interaction with the reference lattice

∏* :

Reduced pressure

kB :

Boltzmann constant

2-pic:

2-(Aminomethyl)pyridine

pyz:

1-Pyrazolyl

pz:

Pyrazine

phen:

1,10-Phenanthroline

ptz:

1-n-Propyl-tetrazole

depe:

1,2-Bis(diethylphosphino)ethane

PM-Bia:

(N-(2′-Pyridylmethylene)-4-aminobiphenyl

bipy:

2,2′-Bipyridine

PM-Aza:

(N-(2′-Pyridylmethylene)-4-azophenylaniline

mtz:

1-Methyl-tetrazole

abpt:

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

bt:

2,2′-Bithiazoline

phy:

1,10-Phenanthroline-2-carbaldehyde-phenylhydrazone

5-NO2-sal-N(1,4,7,10):

5-NO2-Salicylaldehyde-1,4,7,10-tetraazadecane

bpym:

2,2′-Bipyrimidine

4-R-trz:

4-Substituted-1,2,4-triazole

hyptrz:

4-(3′-Hydroxypropyl)-1,2,4-triazole

hyetrz:

4-(2′-Hydroxy-ethyl)-1,2,4-triazole

4,4′-bipy:

4,4′-Bipyridine

azpy:

4,4′-Azopyridine

btr:

4,4′-Bitriazole

btre:

1,2-Bis(1,2,4-triazol-4-yl)ethane

bpb:

1,4-Bis(4-pyridyl-butadiyne)

btzb:

1,4-Bis-(tetrazol-1-yl)butane-N1,N1′

py:

Pyridine

bpe:

trans-1,2-Bis(4-pyridyl)ethylene

cat:

Catecholato

sq:

Semiquinonato

phendiox:

9,10-Dioxophenanthrene

cth:

dl-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane

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Acknowledgements

We thank the European Commission for granting the TMR-Network “Thermal and Optical Switching of Molecular Spin States (TOSS)”, Contract no. ERB-FMRX-CT98-0199EEC/TMR. Financial support from the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie and the Materialwissenschaftliches Forschungszentrum of the University of Mainz is gratefully acknowledged. A.B.G. is grateful for a fellowship from Alexander von Humboldt Foundation. We thank Prof. J.A. Real for making available structural data and Dr. H. Spiering for his critical reading of the manuscript.

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  1. Institut für Anorganische Chemie und Analytische Chemie, Johannes Gutenberg Universität, Staudinger Weg 9, 55099, Mainz, Germany

    Vadim Ksenofontov, Ana B. Gaspar & Philipp Gütlich

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  1. Vadim Ksenofontov
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  2. Ana B. Gaspar
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  3. Philipp Gütlich
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Ksenofontov, V., Gaspar, A.B., Gütlich, P. Pressure Effect Studies on Spin Crossover and Valence Tautomeric Systems. In: Spin Crossover in Transition Metal Compounds III. Topics in Current Chemistry, vol 235. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b95421

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  • DOI: https://doi.org/10.1007/b95421

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-40395-1

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