ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2015, Vol. 89, No. 7, pp. 1254–1262. © Pleiades Publishing, Ltd.

, 2015.

STRUCTURE OF MATTER
AND QUANTUM CHEMISTRY

Spectroscopic Study of Copper(II) Complexes with Carboxymethyl

Dextran and Dextran Sulfate1
S. Glišića, G. Nikolića, M. Cakića, and N. Trutićb
a
Faculty of Technology, University of Niš, RS-16000 Leskovac, Serbia
b Faculty of Medicine, University of Niš, RS-18000 Niš, Serbia

e-mail: slobodanglisic88@open.telekom.rs
Received July 14, 2014

Abstract—The copper(II) ion complexes with carboxymethyl dextran (CMD) and dextran sulfate (DS) were
studied by different methods. Content of copper was determined by atomic absorption spectroscopy. It was
found that copper : ligand mole ratio (Cu : CMD) is 1 : 2, and Cu : DS is 1 : 1 by mole ratio method. Spec-
trophotometric parameters of synthesized compounds are characteristic for Cu(II) ion in octahedral (Oh)
coordination. Analyzing of FTIR spectra in ν(C=O) vibration region has showed that –COOH group acts as
bidentate ligand, while the compounds of Cu(II) with DS copper ions are in the region of four oxygen atoms
of two adjacent sulfo groups. The presence of crystalline water was determined by isotopic substitution of H2O
molecules with D2O molecules. Comparison of spectra recorded at room (RT) and liquid nitrogen tempera-
ture (LNT) has enabled detection bands of water molecules libration indicating that they are coordinated
complementing coordination sphere of Cu(II) ions to six. The complexes are of Cu(II) · (CMD)2 · (H2O)2 or
Cu(II) · DS · (H2O)2 type. The similarities of the γ(C–H) range in a part of FTIR spectra indicate that there
is no difference in the conformation of the 4C1 glucopyranose (Glc) unit CMD and DS synthesized Cu(II)
complexes.

Keywords: dextran sulfate, carboxymethyl dextran, copper complex, AAS, FTIR, UV–VIS.
DOI: 10.1134/S0036024415070122

INTRODUCTION complex compounds demonstrate the lower level of

Copper is an essential component of biological sys-
tems. Copper participates in miscellaneous processes
(forming hemoglobin, carbohydrate metabolism, cat-
echolamine biosyntheses, antioxidant protection of
organism, etc.) throughout a number of enzyme sys-
tems [1, 2]. A reduced insertion of copper or disrup-
tion of copper level in organism leads to the appear-
ance of many diseases, such as hypochromic and
microcytic anemia. Adding preparation on an inor-
ganic copper salt basis causes corrections of the patho-
logical state [3, 4]. The therapy of the diseases includes
the usage of preparations on inorganic copper salt
basis or copper complex compounds with organic
ligands. Literature brings descriptions of copper com-
plexes with hydrated derivates of low molecular dex-
tran and pullulan [5]. Copper ions along with these
ligands form an octahedral complex compound type,
the composition of which is changing in correlation
with reaction terms of synthesis, thus forming complex
compounds CuL2 · 2H2O in neutral, CuL2 ·
(H2O)(OH), in weakly alkaline area (10–12 pH), and
CuL2 · (OH)2 in strong alkaline area [5–10]. These
1 The article is published in the original.
toxicity and better reabsorption in comparison to the
commercial preparations with an inorganic copper
salts, and therefore they can be used for the design and
optimization of medicines within the treatment of
copper insufficiency [11].
Dextran derivates (Fig. 1), such as carboxymethyl
dextran or dextran sulfate, contain one or more either
carboxyl or sulfo-groups, therefore integrating the
conditions for forming complex compounds of differ-
ent composition and coordination with copper ions
Cu(II). It is expected that complex compounds CMD
and DS can form complex compounds with various
ratio of metals and ligands, or mixed complex aquatic
and/or hydroxyl compounds. There is insufficient
information about the synthesis and analysis of this
kind of complex compounds. Jezierska et al. [12] have
been analyzed complex compounds of Cu(II)-ion
with dysfunctional polymers containing amino and
carboxyl groups. ESR technique have been used for
the confirmation of complex compound formation, as
well as for comparing donor abilities between amino
and carboxyl groups. Bartkowiak et al. [13] have been
analyzed ESR spectra of dextran and carboxymethyl
dextran gels mixtures in function of pH, aiming at
functional groups identification, which are included

1254
 SPECTROSCOPIC STUDY OF COPPER(II) COMPLEXES
(a)
6
CH2 OH 2 OH H
O 5 1 CH2
H OH
H H H 3
4 1 O H O HO
OH H H
3 H
2 O
NO CH2 5
H
O 6
H
H2C
CH2
O C O C
HO
HO
Fig. 1. Molecular structure of CMD (a) and (b) dextran sulfate sodium salt (DS).
in complexion with Cu(II)-ion. The results of the ESR
analysis have shown that within complex compound
formation including Cu(II)-ion, there exists a partici-
pation of carboxyl and deprotonated hydroxyl group of
ligands. ESR spectroscopic technique, Ajiboye et al.
[14], have been used for studying of Cu(II)-ion com-
plex compounds with celluloses. ESR parameters
showed that Cu(II)-ion is in quadratic-planar or
tetragonal deformed coordination by the O-atoms of
ligand. Other spectroscopic, more detailed analysis,
have indicated that every Cu(II)-ion in a complex
compound has been coordinated with two glucopyra-
nose cellulose units.
Considering the potential usage of this kind of
complex compound types in pharmacy, this work
presents the results of physico-chemical and spectro-
scopic analysis of copper complex compounds con-
taining CMD and DS, synthesized in neutral area
(pH ≈ 7), using AAS, UV–VIS and FTIR, D2O-FTIR,
and LNT-FTIR spectroscopic methods. Through
these methods, there can be accomplished a quite good
insight in the stoichiometry of complex compounds,
the manner of binding metals and ligands, the confor-
mation of glucopiranose and the way of binding water.
Complex compounds are synthesized in neutral area,
similar to Cu(II) complex compounds containing dex-
tran and pullulan, hence that kind of complex com-
pound has the best pharmacological properties [15].
EXPERIMENTAL
Synthesis of complexes. A solution containing
2 mmol of ligand CMD (PCI “Zdravlje” Leskovac,
Mw = 100000 g/mol) or DS (Sigma Aldrich, Sweden,
Mw = 500000 g/mol, 17% S) in 100 mL of H2O, was
added dropwise a solution containing 1 mmol of
Cu(CH3COO)2 · H2O (copper acetate monohydrate),
with continuous stirring (10 and 60 min) to a pH about
7 is reached. The change of solution color from blue to
green indicated that the synthesis of the complexes was
completed. The reaction mixture was then cooled to
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1255
(b)
OH CH2
H
OH
4 SO3Na H H
O SO3Na H
H SO3Na O
SO3Na H SO3Na
SO3Na n
n
room temperature, and the complex was precipitated
by addition of 50 mL 96% ethanol. After overnight
standing, the ethanol was decanted, and precipitate
was redissolved by redistilled water. The dialysis of
solution was used to remove unbounded ions. Finally,
the complex was precipitated from dialyzed solution
by 96% ethanol and after decantation dried for 3 h at
105°C in a vacuum oven.
Atomic absorption spectrometry (AAS). The copper
content has been determined by the AAS method on
the Philips PYE UNICAM SP 9 spectrometer at the
Institute for Public Health, Leskovac. The measure-
ment is conducted at 324.8 nm, aperture width 0.5 nm
in acetylene-air flame with Cu hollow cathode lamp.
UV–VIS spectroscopy. Absorption spectrum (and
other analyses conducted using methods of UV–VIS
spectrophotometry) has been recorded on spectro-
photometer Varian Cary-100 Conc. UV–VIS in wave-
length region of 190–900 nm in quartz cuvettes (1 × 1
cm), at room temperature, against re-distillated water.
The computer processing of the recorded HP-GPC
chromatograms and UV spectra has been conducted
using Cary UV-Conc software (Copyright©, Varian
1999).
For determining the ratio of metals and ligands by
Cu–CMD, according to Jobb’s method, solutions
have been prepared; 0.0995 g copper acetate monohy-
drate has been dissolved in 50 mL of water and pri-
mary CMD solution 0.119 g in 50 mL of water. From
these solutions, a series of solutions has been com-
posed by mixing primary solutions in different mole
ratios, and the absorbance measurements have been
conducted at 279 and 744 nm.
Since preliminary analyses has showed that the
complex compound Cu–DS is unstable for determin-
ing the ratio of metals and DS, a mole ratio method
has been conducted. The following solutions have
been prepared; copper acetate 0.050 g dissolved in
100 mL of water and primary DS solution 0.110 g in
100 mL of water. The measurement of the absorbance
of the solutions with different mole ratios, which have
Vol. 89 No. 7 2015
1256 GLIŠIĆ et al.
Physico-chemical properties of complex compounds
Cu, %
Complex Yield, %
10 min 60 min
Cu–CMD 6.1 12.1
Cu–DS 2.5 12.5
been prepared in such a way that in the same volume
of the solution was added a different amount of vol-
ume of the DS solution, has been conducted at 215,
254, and 698 nm.
FTIR spectroscopy. For recording IR spectra of the
solid samples, the method of pressing substance along
with KBr has been conducted. IR spectra of the solid
samples have been recorded immediately after prepar-
ing pastille at room temperature, RT (289 K) and the
temperature of liquid nitrogen, LNT (77 K) on FTIR
spectrometer BOMEM MB-100 (Hartmann and
Braun, Canada), which is equipped with a standard
(deuterated triglycine sulfate/KBr) DTGS/KBr
detector, in region of wavelength numbers mid-IR
from 4000–400 cm–1 and the resolution of 2 cm–1,
with a reference pastille prepared from pure KBr
(150 mg, Merck). Nitrogen gas is blown through spec-
trometer, in order to remove humidity and CO2, which
have a negative effect on IR spectrum quality.
For recording FTIR spectrum at liquid nitrogen
temperature “LNT–FTIR spectrum” was used a
Graseby Specac P/N 21525 cell with variable tempera-
ture. The computer processing of the recorded IR
spectra has been conducted in software application
Win-Bomem EasyTM 3.01 C Level II (Copyright©
1991–1994, Galactic Industries Corporation) under
Windows XP OS platform.
The method of isotopic exchange. The isotopic
exchange of molecule H2O with molecules D2O has
been performed in a so-called hydro-thermal manner,
where synthesized D2O complex stands in a glass
ampoule on increased temperature at about 40°C, for
a 10-day period.
RESULTS AND DISCUSSION
Some physico-chemical properties of the synthe-
sized complex compounds are presented in table.
The results presented in table refer to the complex
compounds derived at boiling temperature and pH ≈ 7.
Within these reaction terms copper content is ana-
lyzed respectively after 10 and 60 min. After 60 min,
achieved yields of compound Cu–CMD 64% and
Cu–DS is about 25%, with the copper content of 12.1
and 12.5%, respectively. The computed ratio for these
copper contents CMD as a ligand and Cu is approxi-
mately 2 : 1, and with compound Cu–DS it is 1 : 1.
These mole ratios has been confirmed by Jobb’s
method for compound Cu–CMD, whereas for com-
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Molar ratio
λmax, nm Color complex
M:L
64.06 1:2 279, 309, 744 Green
25.06 1:1 254, 698 Green
pound Cu–DS has been used mole ratio method. The
success of synthesis has been monitored through color
changes, where blue has turned in green. The green
color of both compounds origins from the energy
absorption from VIS fraction of the spectrum, and as
a consequence of d → d transition indicates that most
likely it is the matter of octahedral copper types.
UV–VIS spectroscopy. The spectra found in UV–
VIS region are illustrated in Fig. 2. Introducing car-
boxymethyl group or sulfo-group as a chromophore
groups to the structure of dextran causes the emer-
gence of CMD and DS, and thus it is expected to find
absorption bands from π → π* transition (at about
180 nm) and n → π* (at about 270 nm). These bands,
most likely because of low intensity, cannot be seen.
However, in complex compound Cu–DS in the wave-
length region of 200–300 nm, there is an intense band
at about 245 nm, and within Cu–CMD at 279 nm,
with the inflection at 309 nm. These bands due to
ligand-metal interactions, i.e., coordinative bond
forming, hence criteria for the synthesis success is cre-
ated. The fact that the absorption maximum of com-
pound Cu–DS is on a shorter wavelength indicates a
stronger bond within Cu–O then within Cu–CMD.
In the visible region of the spectrum there occurs a
broad band within Cu–CMD, λmax = 744 nm, and for
Cu–DS at 698 nm. These bands can be accounted to
transition of d → d type in the central metal copper ion
with configuration Cu2+: [Ar] 3d9. By the quantum
mechanics rules, d → d transition is forbidden, and the
facts show that it exists. This digression is occurring
due to the combination of the wavelength functions d-
and p-orbitals, in cases where a molecule as a entity
does not have a center of symmetry, and their symme-
try is disturbed by implementation wavelength func-
tions which refer to the vibrations of the ligands. If we
presume that the interaction of d-orbitals M(II)-ion
probably occurs with p-orbitals, then transition d → d
is actually p → d transition, which is allowed by the
quantum mechanics rules of choice. According to lit-
erature data, the bigger mixing of correspondent d-
and p-atom orbitals (pπ–dπ interaction)—the greater
intensity of the correspondent band [16, 17]. The cal-
culated splitting energy of the crystal field, according
to relation: ∆ = ν × 1.2938 × 10–4 = 1.2938 × 10–4 /λ is
1.74 eV for compound Cu–CMD, and 1.83 eV for
compound Cu–DS, and according to relation Em =
hνNA = hcNA/λ = 6.62 × 10–34 (J s) × 3 × 1017 (nm s–1) ×
6.02 × 1023 (mol–1)/λ = 1.197 × 105/λ (nm) =
Vol. 89 No. 7 2015
 SPECTROSCOPIC STUDY OF COPPER(II) COMPLEXES
Abs.
3.2
CMD
2.8 DS
2.4
2.0
1.6
1.2
0.8
0.4
0
200 300 400 500
Fig. 2. UV–Vis spectra of CMD, DS, and their complex compounds.
160.89 kJ mol–1 for compound Cu–CMD, and
171.49 kJ mol–1 for compound Cu–DS. These values
pinpoint tetragonally deformed complex compounds
of the octahedral coordination with six O atoms.
FTIR spectroscopy. The analysis of infrared spectra
of synthesized compounds has been accomplished in
an empirical manner—on the basis of literature data
and internecine comparison of spectrum to referenced
dextran compound, carboxymethyl dextran and com-
plex compounds. The infrared spectrum of dextran
has been the subject of numerous analyses [6, 8, 18–
23]. By researching the spectrum regions of dextran, the
data concerning the content of α-1.6 bond can be
obtained (but also concerning other bonds α-1.3, α-1.4)
which is very important information regarding linearity,
and also regarding the grade of polymer bifurcation,
grade of crystallinity, conformation of glucopyranose
units (which, as known, has six forms), conformation
transition and changes in the chemical structure or
some other way changed dextran.
Accordingly, if dextran is to be chemically treated
in such a manner that OH groups eterificate (as with
CMD) or esterificate (like with DS), we obtain prod-
ucts whose spectra is to differentiate from referenced
dextran. By introducing carboxymethyl groups (reac-
tion of dextran with chloroacetic or bromoacetic acid
in an alkaline media), we obtain carboxymethyl dex-
tran in whose FTIR spectrum, unlike the one of the
referenced dextran, bands from all types of vibrations
of carboxymethyl group are expected: band from
ν(C=O) vibration at proximately 1740 cm–1; band from
deformed δ(C–OH) vibration which appear at
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1257
Cu−CMD
Cu−DS
0.08
0.06
0.04
0.02
0
600 700 800 900
600 700 800 900
λ, nm
approximately 1250 cm–1; band from ν(C–O) vibra-
tion at proximately 1150 cm–1 and band from deformed
δ(C=O) vibration at approximately 680 cm–1.
Only the first vibration band can be found in liter-
ature [24], and as for the other bands, which are
important for following complexion method FTIR
spectroscopy, there are no such data. The comparison
between dextran spectrum and CMD, which are dis-
played on (Fig. 3), shows that in the CMD spectrum
there reside bands at approximately 1740, 1244, 1140,
and 682 cm–1, (these are marked by arrows) which
cannot be found with dextran, so they can be accred-
ited to the aforementioned vibrations.
The intensity and location of the bands, which are
derived from vibrations of all types of hydroxyl dextran
groups in CMD spectrum, should be decreased,
depending on the etherification (esterification)
degree, which can be perceived in the region ν(OH)
approximately 3400 cm–1 and δ(OH) vibration, 1400–
1100 cm–1.
The presence of sulfo-group in DS spectrum can be
determined based on the bands that are present in the
FTIR spectrum around approximately 1260 and
988 cm–1, which are respectively derived from
νas(S=O) and νs(S=O) vibrations, and bands around
approximately 809 and 580 cm–1 that are respectively
derived from νas(O–S–O) and νs(O–S–O) vibrations,
[25–28], as the Fig. 4 shows. When a sulfo-group is in
an axial position, the band occurs at 850 cm–1, while
for equatorial position it is at 820 cm–1. Based on these
criteria, it can be assumed that the sulfo-group ana-
Vol. 89 No. 7 2015
1258 GLIŠIĆ et al.
T, %
a
4000 3000
Fig. 3. FTIR spectrum of (a) dextran and (b) CMD.
lyzed DS in equatorial position is in the glucopyranose
ring.
The comparison between CMD and DS spectra, as
complexion ligands with spectra of their complex
compounds with copper ions, can give us some infor-
mation on the synthesis success, structural geometry
and possibly configured chelation rings, but also on
the conformation of glucopyranose unit and the man-
ner of binding water. Anion CMD or DS can form
compounds with metal cation for which, as far as the
structure is concerned, there are two possibilities:
either metal complexes are ion built (their spectrum
looks like the spectrum of DS sodium salt) or, in case
they are chelates, where the nature of configured che-
lation rings could be similar to complex compounds of
β-diketone, when the bond order of C–C, C–O, and
M–O is either completely equal or completely differ-
ent. A good indicator of the binding and nature of con-
figuring chelation rings could be region CO/SO vibra-
tions of all types of complex compounds.
FTIR spectrum of CMD complex compound,
including Cu(II)-ion that has been recorded at room
temperature, is show in (Fig. 4). There are no bands in
Cu–CMD complex spectrum, neither from deformed
δ(C–OH) (1250 cm–1), nor from the valence ν(C–O)
vibration (1150 cm–1) nor from the deformed C=O
vibration, which can be a good indicator of the synthe-
sis success. Moreover, in the region of ν(CO) vibra-
tions, there is one broad intense band, at approxi-
mately 1603 cm–1 and another one of somewhat less
intensity at about 1430 cm–1. These bands, according
to their position, shape and intensity should be
attributed to the asymmetrical and symmetrical
valence vibration of C=O group, the order of which
has been changed in relation to reference compound
CMD. Within the high frequency, CMD vibration at
approximately 1740 cm–1 predominantly contributes
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
2000 1000
ν, cm−1
to valence C=O vibration, while within low frequency
CMD vibration at approximately 1150 cm–1 valence
ν(C–O) vibration. This would have meant that at the
coordination within complex compound configura-
tion C=O are participating with free electron pair and
–OH group that is derived from COOH, across which
covalent bond –O–M is formed. Frequency of νas and
νs(C=O) vibration depends on the coordination of the
metal ion with carboxyl group from ligands. On the
basis of the FTIR spectra in ν(CO) vibration area
information about ligand identicity can be obtained
(monodentate, bidentate, bridge–ligand), mode of
coordination to the metal ion, the type of donor
atoms, as well as the type of the complex (mononu-
clear, binuclear and polynuclear) [29–33]. On the
basis of these data the difference in frequency of
175 cm–1 between νas and νs(C=O) vibration in FTIR
spectra of Cu–CMD shows that CMD carboxyl group
is acting like a bidentate ligand and it is understand-
able that, due to electron delocalization, order of
bonds is changing from ligand to the complex com-
pound.
FTIR DS spectrum, in the form of sodium salt,
and its compound with copper ions are basically simi-
lar (Fig. 4). There is a difference in region νas and
νs(SO) vibrations, which are weakly lower (about
15 cm–1) in complex spectrum on the one hand, on the
other hand, because in the compound spectrum con-
taining copper there exists a clearly separated band at
approximately 1420 and 1350 cm–1. That fact can serve
as an indicator of the synthesis success. The similarity
of the spectra, however, depicts similar structure; in
other words, this compound has predominantly ionic
character.
Very important changes can be observed in the
range of 1500–1300 cm–1 by detailed empirical analy-
Vol. 89 No. 7 2015
 SPECTROSCOPIC STUDY OF COPPER(II) COMPLEXES 1259

T, %
a

919.059
2928.09

1325.7

1152.57
1096.21
1414.27

1007.63
3439.41

1603.5
b

2948.22

745.936

584.891
826.458
1160.62
1647.78

983.477
3443.43

1019.71
1261.28
c

741.91
677.492
580.865
810.354
1160.62
1349.85
2948.22

1426.35

983.477
1249.2

1023.74
1627.65
3455.51

4000 3000 2000 1000

ν, cm−1

Fig. 4. FTIR spectrum (a) Cu–CMD, (b) DS, (c) Cu–DS.

sis. The bands at about 1460 and 1370 cm–1 from δ(C–
H) vibrations are characteristic for one of more possi-
ble positions of the CH2–O group, rotating around the
C5–C6 bond of the glucopyranose unit. The change
of the angle between the methylene group and the
polysaccharide chain axes consequently decreases the
intensity of the appropriate IR bands ν(C–H) and
δ(C–H) vibration. The Cu(II) ions in solution have a
possible influence on the rotation of the CH2–O
groups in the complexes [18].
The area of deformational CCH vibrations out of
plane surface from 1000 to 700 cm–1 coupled with C–
C–O, O–C–O, and C–O–C vibrations are especially
important for structural analysis of polysaccharides,
their derivates and compounds with M(II)-ions,
because it provides information about the type of gly-
coside bond and the conformation of monosaccharide
(glucopyranose) unit [6, 23]. In this way, for
α-1.6 bonds in this area, there are two bands of
medium intensity, one at approximately 916 cm–1 and
the other at approximately 765 cm–1. If β-D-glycoside
bond is to be formed, then the spectral image in this
area is different, and there is one band at 896 cm–1 and
if there are α-1.4 bonds—then there are spectral
images at 759 ± 3 and 730 ± 5 cm–1.
In CMD DS spectra and the spectra of their com-
plex compounds with Cu(II), this area γ(C–H) con-
tains bands at approximately 920, 760 and approxi-
mately 850 cm–1. According to the premises criteria, it
could be concluded that within all of the compounds
there participates a 4C1 conformation glucopyranose
unit, which means that in the flow of complex synthe-
sis there are no conformation crossings, but also the
ligands and complex compounds with high content of
the α-1.6 bonds, which indicates high linearity of the
polysaccharide ligand.
Having in mind the results of physico-chemical
UV–VIS analyses, according to which the ratio of the
ligands CMD and Cu(II) ions is 2 : 1, and 1 : 1 with
Cu–DS compound—tetragonally deformed octahe-
dral coordination and the bidentate of the ligand, the
coordination sphere of copper is to be filled up to
coordination number six. This can be achieved by
eater molecules or some other ions present in the sys-
tem. In the case of water presence, it is expected to
obtain bands from vibrations of all kinds of water. In
the region of ν(OH) vibrations of water molecules,

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 7 2015

1260
(a)
T, %
RT
2928.09
LNT
3439.41
2939.12
Fig. 5. RT and LNT spectrum of CMD partially deuterated hydrate analog (a) and δ(HOH) region (b).
approximately 3600 cm–1, all spectra will show a broad
intense band with multiple inflections, with lower-
and higher-frequency side, so it is very difficult to
locate this vibration by the sheer appearance of this
area, because except it, there can be found bands form
ν(OH) vibrations –OH groups of glucopyranose units,
in which case it can be helpful to find the comparing
spectra of eventual hydrates and their deuterated ana-
logs, the spectrum of which can contain bands from all
types of vibration of water molecule at lower frequen-
cies with the movement factor of about 1.4. In spec-
trum area ν(HOD) vibrations of a partially deuterated
Cu–CMD hydrate analog, shown in (Fig. 5a), there is
a band at approximately 2510 cm–1, the partner of
which in ν(HOH) area, considering the factor of
movement 1.34, is to be at approximately 3400 cm–1,
but its exact location is difficult to determine, due to
the overlapping with the ones from ν(OH) vibrations.
The presence of the band of the deuterated analog
from ν(HOD) vibrations confirms the presence of
water in the structure of this compound.
As known, Falk et al. [34] have suggested criteria
according to which, based on studying protonated
spectrum partially and completely deuterated
hydrates, it is possible to determine the number of
H2O (n) molecule types, as well as a number of non-
equivalent OH groups in them (m). According to these
criteria of the band appearance in ν(HOD) area, it is
obvious that both in a carboxymethyl dextran struc-
ture and its complex compound containing Cu(II)
ions structure, there is, probably, one crystallographic
tape of water molecule, n = 1. Based on Berglund’s
et al. correlation [35], it is possible to estimate the
strength of the hydrogen’s bond, which has been
formed by water protons, i.e., Ow⋅⋅⋅O distance:
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
GLIŠIĆ et al.
(b)
RT
2513.4
LNT
2505.35
1603.44
1636.42
ν, cm−1
ν(HOD) = 2727–8.97 × 10 6e −3.73R(O w O). Based on the
frequency of ν(HOD) vibration, 2510 cm–1, the esti-
mated Ow⋅⋅⋅O distance is to be 280 pm with Cu–CMD
complex compound.
The affirmation of crystal water existence is the
region around 1600 cm–1, which is sensitive to tem-
perature decreasing, as it can be seen in (Fig. 5b). The
temperature decreasing causes changes in the position
and configuration of the band at approximately
1600 cm–1, which has complex structure, and those
changes are attributed to νs(C=O) vibration, in other
words, band has multiple inflections. This can be the
result of overlapping with δ(HOH). The temperature
decreasing causes clear separation between the two
bands, with one of them not changing its position
(1600 cm–1, νas(C=O)) and the other moving towards
higher frequencies, so it can be attributed to δ(HOH)
vibration, and since frequencies higher than 1600 cm–1
belong to constitutional water and coordinated water,
and not a absorption water [36, 37]. Studying the low
frequency parts of the spectrum can provide an answer
concerning the type of water in question. The differ-
ence in the hydrate spectrum appearance with coordi-
nated and uncoordinated water within the structure
actually means that within the compound containing
coordinated water at low frequent region of the spec-
trum, bands from so-called water libration, rocking,
twisting, wagging, are also expected. Usually, two
bands appear, one at 1000–600 cm–1, and the other at
600–400 cm–1.
On one hand, bands from these librations are of a
lower intensity, whereas on the other hand this area
includes bands from other types of vibrations, so locat-
ing them is difficult, but since their intensity and loca-
Vol. 89 No. 7 2015
 SPECTROSCOPIC STUDY OF COPPER(II) COMPLEXES 1261

(a) (b)
T, %
RT

850.61

687.80
613.82
913.10
LNT

706.73
763.15
RT
705.67
911.62

765.51

ν, cm−1

Fig. 6. RT and LNT FTIR spectrum of Cu with (a) CMD and (b) DS.

tion are sensitive to temperature decreasing, compar- four O atoms from two carboxylic groups of two poly-
ing spectra recorded at room temperature RT and meric chains and two O atoms, from two coordinated
LNT can enhance their detection. According to these molecules of water as it shown in (Fig. 7). In Cu–DS
criteria, in Cu–CMD spectrum of decreased tem- complex, probably Cu(II) ions are in the region of four
perature we can expect candidates for this librations in O atoms of the two adjacent sulfo groups of the same
the form of bands at approximately 860, 770, 660 cm–1 monomer units, and two O atoms from two coordi-
(Fig. 6a), and within Cu–DS at approximately 660 nated molecules of water.
and 610 cm–1 (Fig. 6b). This fact refers to the existence In low frequency area, in region smaller than
of probably two coordinated water molecules, which 600 cm–1 bands from complexes M–O valences are to
complement coordinate sphere of Cu(II) up to six, the be expected, and their position is to be sensitive to the
protons of which are included in the formation of rel- nature of the metal itself, however, due to the weak
atively weak hydrogen bonds. Taking into account the bands from deformated vibrations of the glucopyra-
stoichiometry of the complex and Oh environment of nose unit in this area, their location cannot be deter-
Cu(II) ions, complex Cu–CMD is formed by depro- mined in an empirical manner.
tonation of monomer unit CMD, so it is in region of
CONCLUSION
Chain 1 Chain 2 Coper content determined by AAS method as well
CH2
as Cu(II) : ligand ratio determination has been shown
CH2 that this ratio is 1 : 2 for Cu–CMD complex, while it
O
H H H O is 1 : 1 for Cu–DS complex. Investigations performed
H H H by UV–VIS spectroscopy have shown that in both
OH H OH H
O O complexes Cu(II) ion surrounded by six oxygen atoms
OH OH tetragonal distorted by Oh structure. Difference in fre-
H n n
O H O quency at 175 cm–1 between νas and νs(C=O) vibration
O H2O O
in FTIR spectra of Cu–CMD shows that CMD car-
H2C C Cu C CH2 boxyl group is acting like a bidentate ligand and it is
understandable that, due to electron delocalization,
O H 2O O order of bonds is changed from ligand to the complex
compound. The similarity of sodium salt of DS and
Cu–DS FTIR spectra indicate that Cu–DS complex
Fig. 7. Structure model of Cu–CMD complex, with six O-
donor atoms in tetragonal distorted Oh environment of is predominantly ionic. A part of FTIR spectra, in the
Cu(II) ions. range 1000–700 cm–1 of Cu (II) ion complexes with

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 7 2015

1262 GLIŠIĆ et al.
DS and CMD, indicates no influence of complexation
process on the conformation change of 4C1 glucopyra-
nose units. The IR band δ(HOH) at 1640 cm–1 indi- 16.
cates water molecules existence in complex structure.
D2O–FTIR in ν(HOD) and δ(HOD) shows presence 17.
of one water crystallographic molecule which protons
are mostly included in relatively weak hydrogen bond-
ing. LNT–FTIR, in the range of water molecule libra- 18.
tions, shows that water molecules are Cu-coordinated
in both complexes, enriching the first coordination 19.
sphere of Cu(II) ions up to six. The complex composi-
tion would be Cu(II) · (CMD)2 ⋅ (H2O)2, i.e., Cu(II) · 20.
DS ⋅ (H2O)2.
21.
ACKNOWLEDGMENTS
This study was supported by Ministry of Science of 22.
the Republic of Serbia Grant TR-034012.
23.
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