UNIVERSITY OF PARIS-SUD, ORSAY

ERASMUS+ TRAINEESHIP
REPORT

Supervisor: Marie-Laure Boillot

Students: Balica Elena
Plesca Diana

2019
Traineeship title: Synthesis and characterization of spin-crossover materials
University: University of Paris-Sud, Orsay
Institut de chimie moléculaire et des matériaux d'Orsay (ICMMO)
Departament : Departament of Chemistry
Period of the mobility: 17.06.2019 - 17.08.2019

Goal of the traineeship:

1. Synthesis of spin-crossover materials:
- FexNi1-x(btr)2(NCS)2 . H2O
- Fe(BF4)2 . 6H2O + 2KTp -> FeTp2+2K(BF4)
- Ni(btr)2(NCS)2 . H2O
- Fe0.74Ni0.26(btr)2(NCS)2 . H2O
2. Caraterization by various physico-chemical methods, including magnetic measurements
using a SQUID magnetometer and optical measurements using a laser and optical fiber

Introduction
Spin crossover is a phenomenon that occurs in some metal complexes wherein the spin
state of the complex changes due the variation of a thermodynamic parameter such as
temperature or pressure or by the application of perturbation like an intense magnetic field or
light irradiation (Light Induced Excited Spin State Trapping). Spin crossover refers to the
transitions between high to low, or low to high, spin states.
Transition metal complexes with d4, d5, d6 and d7 electron configurations usually are
capable of forming either spin-free (high spin, HS) or spin-paired (low-spin, LS) ground
states, depending on the strength of the cubic ligand field, ∆ (or 10Dq), relative to the mean
spin-pairing energy, Π. The simple inequality
∆(HS)<Π<∆(LS)
expresses the conditions for finding a particular transition metal complex with either HS
behaviour (complexes with weak ligand fields ∆<Π) or LS behaviour (complexes with strong
ligand fields ∆>Π). Intermediate-spin (IS) ground states are rarely encountered; only a few
examples have been reported, e.g. iron(II) complexes with strong axial distortions.
High-spin <-> low-spin electronic spin crossovers may be observed in a number of
transitions metal complexes when the ligand-field and electron-pairing (spin-pairing) energies
happen to be comparable in magnitude.
For an iron(II) ion in octahedral environment, the HS <-> LS crossover can be
represented as:
(t2g)4(eg)2 <-> (t2g)6 or 5
T2g <-> 1A1g
In this case, the potential energy curves of the two electronic isomers present the
following relative characteristics (Figure 1): with regard to the LS form well, the HS form
well is :
 i. Shifted horizontally by ∆R, the metal-ligand bond-length variation associated with the
spin change
ii. Shifted vertically by ∆E = ∆H = HHS – HLS > 0 (H denoting molar enthalpy), which is
weak, of the order of RT

Figure 1: Potential energy curves

In a few rare situations, ∆≃Π, and both the high-spin and the low-spin electronic states
may be thermally populated. Because the 1A1g state is diamagnetic and the 5T2g state is
paramagnetic, the spin equilibrium process can be conveniently monitored by variable-
temperature magnetic susceptibility studies.

FexNi1-x(btr)2(NCS)2 . H2O

….
For the preparation of the FexNi1-x(btr)2(NCS)2 . H2O we used two materials:
- x=0 , M=465.4 gmol-1
- x=0.96 , M=462.4 gmol-1

Figure 2: Graph of the chemical percentage vs the one found in the solid solution (x chim = 0.74 for
obtaining x = 0.68 and ∆T = 10 K wide hysteresis)
 Sample Weight (mg) Mmol (gmol-1) n (moles)
x=0 50.4 465.4 0.000108
x=0.96 168.2 462.4 0.000364

First, we introduced water in a flask and boiled it at 70 – 78 ℃ for approximately one

hour and then we added argon for removing all O2. After we put the two materials in a
schlenk with a magnetic stirrer and a small amount of ascorbic acid to make sure that there is
no more oxygen left. We used argon for transferring the boiled water from the flack into the
schlenk. Then, we put the schlenk with the mixture into the oil bath to boil it in order to get
the crystals dissolved.
Because the Ni crystals could not be solved with just water, we added 1.89 mL of HCl
(after degassing it using argon). That did not work as we expected and we had a negative
result.

Fe(BF4)2 . 6H2O + 2KTp -> FeTp2+2K(BF4)

Volume of THF
Sample Mmol (gmol-1) Weight (mg) n (mmoles)
(mL)
Fe(BF4)2 . 6H2O 337 134 0.39 5
K+[HB(pz)3]- 252.13 200.3 0.79 10
THF (50mL)

First, we distilled and degassed 50 mL of THF, and after we put it in a schlenk. In the
schlenk we introduced argon and vacuum in order to eliminate the O2. In another schlenk we
introduced the two materials with a magnetic stirrer, a small amount of ascorbic acid, argon
for removing O2 and the THF for solubilizing the mixture. It is stirred for 60 min at 293K
(Figure 3 (a)) and then we separated the K+(BF4)- salt (white) from the filtrate by the filtration
under argon. The THF of the filtrate is evaporated under vacuum. We collected at the end
0.1586g of Fe(Tp)2 (pink) (Error! Reference source not found. (b)).
FeC18H20N12B2 – M = 481.90 gmol-1
C – 44.86%; H – 4.18%;
N – 34.88%; Fe – 11.59%;
B – 4.49%
n = m/M
n = 0.1586g / 481.90gmol-1 = 0.33 mmol
(85%) a) b)
Figure 3: a) FeTp2+2K(BF4) solution;
b) FeTp2 crystals
 For analysing the dependency transmittance function of wavenumber for FeTp2, we
used an infrared (IR) spectrophotometer (Figure 4 (a)). First, we measured the background
spectrum, then we mixed the compound (1 mg) with KBr (99 mg), pressed it using a presser
and vacuum (Figure 4 (b)) and introduced the sample (Figure 4 (c)) in the spectrophotometer.

a) b) c)
Figure 4: a) IR Spectrophotometer; b) Presser ; c) Sample of FeTp2

Figure 5: a) Dependency transmittance function of wavenumber for FeTp2; b) Comparison between

the FeTp2 spectrum and the KBF4

In Figure 5 (a) we have the dependency transmittance function of wavenumber for

FeTp2. To identify if the compound still had traces of KBF4 we analysed also the spectrum of
KBF4, then compared them (Figure 5 (b)) and got to the conclusion that our compound does
not have traces of KBF4.
We measured the absorption spectra as function of temperature for the background and
for FeTp35Me2_serie2_sample4 at RT, -66˚C, -138 ˚C,-160 ˚C,-168 ˚C and -172 ˚C using a
UV-VIS spectrophotometer (Cary 3500).
At the RT we observed HS state and at -168 ˚C and -172 ˚C LS state. We plotted the
data that we have collected and did some graphs showing the dependency absorbance function
of wavelength for each temperature (Figure 6). In this dependency, we can see that we don’t
have hysteresis material.
a) b) c)

d) e) f)
Figure 6: Dependency absorbance function of wavelength for FeTp35Me2_serie2_sample4 at RT (a),
-66 ˚C (b), -138 ˚C (c),-160 ˚C (d),-168 ˚C (e) and -172 ˚C (f), where blue is for heating and red is for
cooling

Ni(btr)2(NCS)2 . H2O

Weight (g) Volume of H2O (mL)

Ni(btr)2(NCS)2 . H2O 0.0116 25
KOH 8.42 150
HCl 37% (10 mL) 110

We put the Ni(btr)2(NCS)2 . H2O in a flask and added a water and a stirrer. Then, we
introduced the KOH and the water in a bottle and the water and the HCl in another one.
Ni(btr)2 → 10-3 mol/L
V = 25 mL
nNi = 10-3 mol/L.25 mL = 25.10-3 mmol;
nbtr = 2.nNi = 2.25.10-3 mmol = 50.10-3 mmol ;
HCl → 1 mol/L
 50∙10−3 𝑚𝑚𝑜𝑙
V= = 50𝜇𝐿 ;
1𝑚𝑜𝑙/𝐿

KOH→ 1 mol/L
50∙10−3 𝑚𝑚𝑜𝑙
V= = 50𝜇𝐿.
1𝑚𝑜𝑙/𝐿

We added into the flask the 50 µL of HCl and the 50 µL of KOH in order to dissolve
the Ni(btr)2(NCS)2 . H2O and then we introduced the flask in a vacuum and evaporated all the
water (Figure 7).

Figure 7: Vacuum

We looked on a microscope at the small crystals that have formed after the
evaporation and saw two colours (white and pale pink) probably corresponding to the KCl
and Ni(btr)x(NCS)2.
For analysing the spectrum of the compound, we used an infrared (IR)
spectrophotometer (Figure 4 (a)). First, we measured the background spectrum, then we
mixed the compound (1 mg) with KBr (99 mg), pressed it using a presser and vacuum (Figure
4 (b)) and introduced the sample (Figure 8) in the spectrophotometer.

Figure 8: Sample of Ni(btr)2(NCS)2

 Figure 9: Dependency transmittance function of wavenumber for Ni (9451) + HCl + KOH

In Figure 9, we can see dependency transmittance function of wavenumber for Ni

(9451) + HCl + KOH, where the first peak (3415 cm-1) corresponds to the H2O, the second one (3117
cm-1) to the H – Carom and the third one (2076 cm-1) to the NCS.

Fe0.74Ni0.26(btr)2(NCS)2 . H2O

Weight (mg)
.
Fe0.96Ni0.04 (btr)2(NCS)2 H2O 107.3
NiCl2 10
KNCS 15

First, we boiled some water using an oil bath and degassed it using argon. Then we
introduced the Fe0.96Ni0.04 (btr)2(NCS)2 . H2O and ascorbic acid in a schlenk, the NiCl2 in a
flask and degassed them. We transferred some boiled water into the flask with NiCl2 to
dissolve it and also some in the schlenk. We put the schlenk into the oil bath and added the
NiCl2 solution. After that, we filtered the mixture and put the filtrate solution in an another
schlenk. Then, we introduced the KNCS into a flask, degassed it, added some water, put it in
the schlenk and let the schlenk under argon.