Physica B 334 (2003) 443450

Electrical conductivity, dielectric permittivity and thermal

properties of the compound aqua[bis(2-dimethylaminomethyl4-NIT-phenolato)] copper(II) including NaCl impurity
F. Yakuphanoglua,*, Y. Aydogdua, U. Schatzschneiderb,1, E. Rentschlerb
a

Department of Physics, Faculty of Arts and Sciences, Firat University, 23169 Elazig, Turkey
b
Max-Planck-Institut fur
an der Ruhr, Germany
. Strahlenchemie, Mulheim
.
Received 25 November 2001; received in revised form 11 March 2002

Abstract
The AC and DC conductivity, the dielectric permittivity and the thermal properties of the compound aqua[bis(2dimethylaminomethyl-4-NIT-phenolato)] copper(II) including NaCl impurity were investigated. The AC conductivity
follows a power law of the frequency sopos : At high frequency, where s is dependent of temperature, the conduction
mechanism is reasonably well interpreted in terms of the correlated barrier hopping model. The DC conductivity
indicates classical semiconductor behavior. So, it is evaluated that the sample is a typical inorganic semiconductor as its
conductivity increases with increasing temperature and the electronic parameters such as activation energy and roomtemperature conductivity are in the regime of semiconductors. It is also found that the dielectric constant and the
dielectric loss values decrease with frequency and increase with temperature. The thermal properties were investigated
under non-isothermal conditions by thermogravimetry (TGA) and differential scanning calorimetry (DSC). The kinetic
parameters such as the order of the reaction, the activation energy (E), enthalpy of formation (DH) and characteristic
temperatures of the exothermic peak were determined by means of the TGA and DSC techniques. The thermal
conductivity shows enhancement with increasing temperature and, in the thermal conductivity mechanism, dominates
transport of electrons.
r 2003 Elsevier Science B.V. All rights reserved.
PACS: 72.80.Le; 77.84.Jd
Keywords: Conductivity; Dielectric permittivity; Metalradical compound

1. Introduction

*Corresponding author. Tel.: +90-424-2370000; fax: +90424-2330062.

E-mail address: fyhan@hotmail.com (F. Yakuphanoglu).
1
Present address: Division of Chemistry and Chemical
Engineering, California Institute of Technology, Pasadena,
California, USA.

In molecular materials science, there is a current

trend to combine physical properties such as
magnetism and electrical conductivity in a synergetic way [1] and this is expected to lead to
materials of high technical interest [2]. In the
metalradical approach to molecular magnetic

0921-4526/03/$ - see front matter r 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-4526(03)00174-1

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F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

materials [3], the exchange interaction between

organic radical ligands and coordinated open-shell
transition metals has been subject of detailed
studies on numerous systems, with a focus on
nitronyl nitroxide radicals due to their stability
and ease of preparation [46], but studies of the
conductivity of these metalradical compounds
have been rather limited. The DC electrical
properties of various inorganic materials have
been extensively studied in recent years, but
relatively little work has been done on their AC
electrical behavior [710]. DC measurements of the
dark current provide information on the conduction processes involved in the material. For
example it is possible to determine whether the
process is electrode or bulk limited by varying the
type of the electrode metal, the applied electric
eld strength and the operating temperature. AC
measurements however yield information which
can be used to determine the conduction process
applicable. Generally speaking, there are three
main conduction models applicable to organic and
inorganic materials: the hopping model, the
variable hopping model and the band theory [7].
In this study, it has been shown that the latter two
processes are applicable to the studied sample by
measuring the frequency dependence of the
capacitance and the dissipation factor, dielectric
constant and also the temperature dependence of
the capacitance and dielectric loss.
On the other hand, the determination of the
thermal properties of solids and liquids is a very
important factor for a variety of technological
applications that involve heat transfer and ow at
high temperatures. In addition, this information
can help in the formulation of liquid equations of
state, in the understanding of the structure of
solids and their behavior, and in the indirect
calculation of related properties, sometimes difcult to obtain experimentally. Calorimetry is a
universal method for study of physical and
chemical transformations in a system where heat
changes occur. The heat capacity, Cp, is one of the
key pieces of information for the design of
chemical reactors. Particularly, in liquid-phase
chemical reactions, Cp data are necessary to
establish the energy requirements for heating and
cooling reactants and products, in distillation to

establish the heat and mass balances occurring in

the columns, and for heat exchangers design [11].
The aim of the present investigation is to
investigate the electrical, dielectric and thermal
properties of the crystalline metalradical compound of the crystalline metalradical compound
aqua[bis(2-dimethylaminomethyl-4-NIT-phenolato)] copper(II) including impurity of NaCl
(Scheme 1) and determine electrical conductivity,
dielectric and thermal parameters of the metal
radical compound such as activation energy,
dielectric constant, conductivity, enthalpy of the
formation, heat capacity, thermal conductivity,
etc.

2. Experimental
2.1. Sample preparation
The Cu(II) complex was isolated as single
crystals and its synthesis, X-ray structure, magnetic dilution studies and ab initio calculations are
described elsewhere [12]. In this study, the metal
radical compound including an impurity of NaCl
was pelletized in a hydraulic press at a pressure of
up to 10 tons.
2.2. Measurements
The electrical measurements were performed
with a Hewlett-Packard multi-frequency LCR
meter in the frequency range of 100 Hz to
1 MHz. The two opposite faces of the sample were
coated with silver paste. Copper wires were
cemented on both surfaces with the paint, and
the sample was mounted on a sample holder, the
temperature of which can be varied over the range
H2O

O
+

O
N
O

N
Cu

O
N

N
O

Scheme 1. Molecular structure of the title compound.

F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

280345 K with a temperature control of 71 K.

The dielectric constant was measured at different
frequencies and temperatures. The thermoanalytical measurements were carried out with Shimadzu thermogravimetry (TGA-50) and differential
scanning calorimetry (DSC-50) instruments. The
complex was heated in a crucible with a heating
rate of 20 /min for the TGA and DSC experiments. The thermal conductivity was determined
by means of the WiedemannFranz law [10].

3. Results and discussion

3.1. DC conductivity
The DC electrical conductivity of the sample
was measured in temperature range of 285345 K
and the conductivity curve is shown in Fig. 1.
Arrhenius behavior is observed in the ranges from
285 to 333 K and from 333 to 345 K, in regions I
and II, respectively. The conductivity data may be
tted to straight lines, where conductivity can be
analyzed by an Arrhenius equation of the form
[1315]:
s s0 exp DE=kT;

where s0 is the pre-exponential factor and DE is

the activation energy for conduction. The activation energy and the pre-exponential factor were
determined for each conduction region as shown

445

Table 1
DC electronic parameters of the compound
DE1 (eV)
0.21

DE2 (eV)
1.06

s01 (S/cm)
2

1.35  10

s02 (S/cm)
1.0  10

11

s25 (S/cm)
3.12  106

in Fig. 1 and are given in Table 1. The activation

energies may correspond to the different energy
levels. These two activation energies are associated
with the intramolecular and the intermolecular
conductivity process. Particularly, the lower values
of DE are associated with the intermolecular
conduction process, while the higher values are
related to the intramolecular conduction process.
In this semiconducting sample, there are two
stages in the movement of carrier motion within
the sample, which are the intramolecular and
intermolecular transfer of the current carrier. In
the intramolecular transfer of electrons, electrons
can hop from one atomic site to another if orbitals
exist at these sites with the same energy levels. In
the case of intermolecular orbital overlap, electrons or holes can travel from one kind of
macromolecule to another. Therefore, p-electrons
can also move from one type of macromolecule to
another by hopping if orbitals with the same
energy levels exist between the complex molecules.
If we assume excited carriers within the molecules,
the carriers are retarded by the barrier macromolecules. The activation energy of the intramolecular conduction process is higher. Therefore,
the rst step of conduction starts between molecules since the lower activation energy corresponds
to intermolecular transfer, while the higher activation energy corresponds to intramolecular transfer. But, basically both processes should be
considered. The intramolecular conduction process occurs between the metal atom and the
ligands in the complex and the intermolecular
conduction process between two macromolecular
complexes [13,15].
3.2. AC conductivity

Fig. 1. DC conductivity of the compound.

The temperature dependence of the AC conductivity of the sample is given in Fig. 2. The

F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

446

this model is given by [21]

p3 N 2 ee0 oR6o
;
4
24
where e and e0 are the dielectric constants of the
material and free space, respectively, and N is the
density of pairs of sites and the hopping length Ro
is given by


1
e2
1
Ro
WM  kT ln
:
5
ot0
pee0

so

The frequency exponent s in the electron CBH

model is evaluated to be
6KT
:
6
s1
WM  kT 1=ot0
Fig. 2. Frequency dependence of the AC conductivity at
different temperatures.

dependence of the real part of the AC conductivity

on the frequency is expressed as follows [1620]:
sAC s0 Aos ;

where s0 is the DC conductivity, and s and A are

characteristic parameters. The exponent s is in the
range between 0 and 1. It has been used frequently
in recent years to characterize the electrical
conduction in different materials. The temperature
dependence of s values is plotted in the inset in
Fig. 2. It is seen that s decreases with increasing
temperature. Therefore, the correlated barrier
hopping model (CBH) is applicable to this sample
[18]. In the CBH model, the electrons in charged
defect states hop over a Coulombic barrier whose
height, W ; is given as
W WM 

ne2
;
pee0 r

A rst approximation of this equation gives the

simple expression [22], s 1  6kT =WM : The AC
conductivity of this sample may be explained quite
satisfactorily by considering these two conduction
mechanisms. With these concepts, a t to experimental data has been made. The values of the
product of N and WM have been adjusted to t
the calculated curves of ln so versus 1=T to the
experimental curves (Fig. 3). Values of WM ; N and
Ro were extracted with the CBH model and are
given in Table 2. The mechanism in the CBH
model is hopping of electrons over the potential
barriers that separate defects, whose sites undergo
lattice distortions upon a change in the electron
occupation. An important difference with other

where WM is the maximum barrier height, e the

dielectric constant of the material, r the distance
between two hopping sites, and n is the number of
electrons involved in a hop (n 1 and 2 for the
single polaron and bipolaron processes, respectively). Also in this model, conduction occurs via a
bipolaron hopping process wherein two electrons
simultaneously hop over the potential barrier
between two defect states and the barrier height
is correlated with the intersite separation via
Coulombic interaction. The AC conductivity in

Fig. 3. AC conductivity of the compound at different frequencies.

F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

447

Table 2
AC electronic parameters of the compound
WM (eV)

0.095

(
Ro (A)

N (m3)

29

1.24  10

0.66

WM1 (eV)

WM2 (eV)

1 kHz

10 kHz

400 kHz

1 kHz

10 kHz

400 kHz

0.75

0.093

0.012

0.53

0.041

theories is the assumption that the barrier height is

correlated with the intersite separation, so W and r
are not independent variables [20].
3.3. Dielectric studies
The frequency dependence of the real part of the
dielectric constant at different temperatures is
shown in Fig. 4. The dielectric constant increases
with decreasing frequency and increasing temperature. The observed variation in the dielectric
constant and the dielectric loss with frequency is
ascribed to the formation of a space-charge region
at the electrode and sample interface, which is
familiarly known as on1 variation, where the
dependence of the space-charge region onto the
frequency is explained in terms of ion diffusion
[23]. The low-frequency region is attributed to the
contribution of charge accumulation at the interface. At high frequencies, due to high periodic
reversal of the eld at the interface, the contribution of the charge carriers to the dielectric constant
decreases with increasing frequency. It is seen that
the values of the dielectric constant increase with
increasing temperature. This shows that the
relaxation frequency of the dispersion increases
with increasing temperature and as a response
moves to higher frequencies. This appears as an
apparent increase in permittivity at a xed
frequency. The effect of increasing frequency on
the dielectric constant is overruled by polarization
and thus a decrease in the value of the dielectric
constant of the system is observed. On the other
hand, the temperature of the dielectric constant for
different frequencies is shown in Fig. 5. It is seen
that at high frequencies the peak (Tp ) in the
dielectric constant shifts to higher temperatures
and the intensity of this peak decreases with
increasing frequency. Such a process is characterized by an asymmetric dielectric loss peak. The

Fig. 4. Frequency dependence of the dielectric constant at

different temperatures.

Fig. 5. Variation of the dielectric constant with temperature of

the compound.

value of the dielectric constant increases with

increasing temperature and the rate of increase is
much faster at 103 Hz than at 2  104 and

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F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

Fig. 7. TGA curve of the compound.

Fig. 6. Plot of the dielectric loss versus frequency of the
compound.

4  105 Hz [24]. This type of behavior may be due

to disordering of the lattice, consisting of a shift of
an ion from one site to another. Although the
disordering of the lattice does not lead by itself to
the appearance of carriers, it substantially facilitates their formation. The reason is that disorder
is accompanied by an increase of dielectric
constant which weakens the Coulomb interaction
between the ion that has departed to another unit
cell and has left a vacancy behind. As a result, with
increasing temperature, a transition from a state of
low dielectric constant into a state of high
dielectric constant occurs [25]. The variation of
the dielectric loss with frequency at different
temperatures is given in Fig. 6. The dielectric loss
decreases with increasing frequency.
3.4. TGA and DSC studies
The TGA and DSC thermograms of the
compound are shown in Figs. 7 and 8, respectively.
The TGA thermogram shows a two-step weight
loss with the evolution of inorganic and organic
fragments. The compound shows thermal stability
up to 210 C and upon heating above 500 C the
corresponding metal oxide remains. The experimental data allow us to suggest that the complex
decomposes in two well-dened steps, involving a
random nucleation mechanism. The change of the
coordination of the metal ion by ligands is

Fig. 8. DSC curve of the compound.

responsible for weakening of the system. Therefore, the complex starts losing weight at lower
temperature and at a faster rate at the rst step
and consequently, the decomposition of the
complex is completed earlier than that of the
ligand. The value of the kinetic parameters and
the mechanism of decomposition were obtained by
using non-isothermal kinetics methods of decomposition. The fractional weight loss (a) and
corresponding 1  an were calculated from the
TGA curves at different temperatures during the
second step of decomposition, where n depends
upon the reaction model. An estimation of the

F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

activation energy of crystallization E may be

obtained with the Stava and Sestak method
[26,27]. This means that the kinetic equation is
n1 ln ln 1  a  2 ln T ln k0 REf
 E=RT;

where k0 is the rate constant, n the order of

crystallization, f the heating rate and E the
activation energy. We have plotted ln ln 1  a
versus 1000=T (Fig. 9) and the activation energy
was determined from the slope of this graph. The
DSC thermogram shows an exothermic peak with
an enthalpy value as given in Table 3. On the other
hand, the value of the heat capacity Cp can be
determined from the DSC thermogram by means
of the relation
q
Cp
;
m DTmax

449

3.5. Thermal conductivity

For the thermal conductivity (k) calculations,
the WiedemannFranz law and the measured
value of s were used. According to the WiedemannFranz law, the thermal conductivity k is
given by [29,30]
k

p2
sT LsT:
3kB =e2

The Lorentz number L is dened as

L

p2
2:45  108 :
3kB =e2

10

where q is the power dissipated through the

sample, m the mass of the sample, and Tmax the
maximum temperature [28]. The heat capacity of
the compound was calculated and is also given in
Table 3.

The thermal conductivity in the different temperature regions were calculated and are given in
Fig. 10. The thermal conductivity is found to
increase with increasing temperature. Because the
complex is a semiconductor, both the motion of
electrons and contributions of phonons determine
the thermal conductivity. However, the thermal
conductivity of the complex is dominated by the
transport of electrons. The value of the activation energy E obtained from the electrical

Fig. 9. Plot of lnln1  a versus 1000=T for the compound.

Fig. 10. Thermal conductivity of the compound.

Table 3
Thermal parameters of the compound
T1 ( C)

T2 ( C)

Tmax ( C)

DH (J/g)

Cp (J/kgK)

E (kJ/mol)

Kbi (W/mK)

187.9

213.3

202.6

388

1915.1

2.817

1.548  105

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F. Yakuphanoglu et al. / Physica B 334 (2003) 443450

measurements makes it possible to estimate the

bipolar contribution to the thermal conductivity.
The bipolar thermal conductivity was calculated
using the equation [30]

2
 3
3p
E
4 ;
kbi
11
LsT
kT
4
where s is the electrical conductivity. When the
electronic thermal conductivity is compared with
the bipolar thermal conductivity, it is seen that the
values of the bipolar thermal conductivity are
higher than the values of the electronic thermal
conductivity due to the activation energy required
for electron transfer.

4. Conclusions
Comprehensive studies of the DC and AC
conductivity, the dielectric permittivity and the
thermal properties of the compound aqua[bis(2-dimethylaminomethyl-4-NIT-phenolato)] copper(II) including NaCl impurity have been performed. The AC conductivity obeys a power law
and can qualitatively be explained by the CBH
model. The dielectric constant and dielectric loss of
the sample decrease with increasing frequency and
increase with increasing temperature. Thus, the AC
conductivity, the dielectric constant and the dielectric loss of the studied compound seem likely to
be both frequency and temperature dependent. The
conduction mechanism of this material also has been
explained by DC conductivity. It is evaluated from
the DC conductivity that the conduction mechanism
is related to inter- and intramolecular conduction
processes in the structure. The DSC results give
thermal stability and heat capacity properties.
As a result, this compound exhibits properties
expected for a typical inorganic semiconductor
with an activation energy DE 0:2121:06 eV and
conductivity at room temperature equal to
s25 3:12  106 S/cm.

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