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6- PREPARATION OF THE COMPOUND [Fe(NCS)2(phen)2]. STUDY OF

THE SPIN CROSSOVER PHENOMENON

Introduction

Octahedral coordination compounds of d-block elements with d4, d5, d6 or d7

electron configurations can present two different electronic ground states,
referred to as the high-spin and low-spin configurations. According to the crystal-
field theory, in the presence of strong-field ligands, the splitting of the d orbitals
(10Dq) exceeds the Coulomb interaction energy caused by the pairing of two P
electrons (10Dq >> P); consequently, the ground state of the compound has a
low-spin configuration. With weak-field ligands, the situation is exactly the
opposite (10Dq << P), and the ground state of the compound corresponds to a
high-spin configuration. If 10Dq ≅ P, then the two configurations may exist in

equilibrium, and their ratio will depend on the temperature, pressure, or other
thermodynamic parameters. The process by which a fraction of molecules
changes its spin is known as spin crossover or spin transition.

The study of the crossover phenomenon and of its associated variations of

physical properties (e.g. changes in colour, metal-ligand distances, dielectric
constants, etc.) represent a hot topic of current investigation worldwide. Hence,
the design of d4-d7 metal complexes, in which the coordinated ligands provide a
value of 10Dq that allows the occurrence of spin crossover via the application of
an external stimulus (like temperature, pressure or light), is of great interest. The
significance of such compounds relies on the considerable number of their
potential applications, like the generation of screens, information-storage
devices, etc.

Octahedral Fe(II) compounds are particularly interesting owing to their d6

configuration since, depending on how the t2g and eg orbitals are populated,
diamagnetic compounds with a ground state of S = 0, or paramagnetic

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compounds with a ground state of S = 2 can be obtained; this type of compounds

may thus be used to develop memory storage devices or sensors.

Experimental Part

Hazards
1,10-Phenanthroline is toxic (T). Methanol is flammable and toxic (F, T). Iron(II)
sulfate is harmful (Xn) and potassium thiocyanate is harmful (Xn).

Experimental procedure
All manipulations must be performed in an inert atmosphere
a) [Fe(NCS)2(phen)2]
A suspension of 0.78 g (8x10-3 mol) of KSCN and 1.04 g (4x10-3 mol) of
Fe(SO4)·6H2O in 30 cm3 of methanol is stirred for 30 min. The coloured solution
is filtered to remove the potassium sulfate that forms (you can use Celite if
necessary). The colour of the solution is due to small traces of Fe3+ ions, which
can be reduced to Fe2+ by the addition of some ascorbic acid. 1.6 g (9 mmol) of
1,10-phenanthroline (phen) in 20 cm3 of methanol is then added dropwise while
stirring. The resulting purple product is isolated by filtration, washed with cold
methanol and dried under nitrogen.

Characterization
• Determine the magnetic susceptibility of the product at room temperature and,
use the susceptibility data provided to calculate cT at temperatures between 2 K
and 300 K.
• Record the IR spectrum (KBr dispersion).
• Observe the change of colour when the compound is cooled with liquid nitrogen.

Report contents

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• A study of the IR spectrum of the compound prepared, assignation of the bands

of the different ligands, and a comparison of the frequencies between the free
ligand and the compound.
• The calculation of the magnetic susceptibility product with temperature (cT) at
each temperature and a graphic representation of the variation of the cT product
and/or magnetic moment against temperature.
• Discussion of the plot obtained. Justification of the variation of the cT product
and/or magnetic moment from room temperature to 180 K, and of the abrupt
change that takes place at this temperature.
• The literature contains crystallographic data on the solid-state structure of the
compound at two different temperatures, namely before and after the transition.
Justify the changes observed and relate them to the electronic configuration of
the compound.

References

CORONADO, E.; BORRÁS-ALMENAR, J. J. (WOOLLINS, J. D., editor), Inorganic

Experiments, VCH, Weinheim, 1994, pàg. 279.

GALLOIS, B.; REAL, J. A.; HAUW, C.; ZAREMBOWITCH, J. Inorg. Chem. 29, (1990),
1152.

GANGULI, P.; GÜTLICH, P.; MÜLLER, E. W.; IRLER, W. J. Chem. Soc. Dalton Trans.
(1981), 441.

KÖNIG, E.; MADEJA, K.; Inorg. Chem. 6, (1967), 48.

GORDON; A. B.; BERRY, J., F. J. Chem. Educ. 85 (2008) 532.

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Additional Material
IR spectra of the complex
[Fe(NCS)2(phen)2]
T%

Crystal structure of [Fe(NCS)2(phen)2]: You can access the structure at the

website of the Cambridge Structural Database with the identifier 167287.
https://www.ccdc.cam.ac.uk/structures/

Magnetic susceptibility: file LQI-6-XvsT.txt in Campus Virtual. Import the data

in Excel or CALC, or any other software to create the cT vs T graph.