Chemical Physics 527 (2019) 110469

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Spectroscopic and electronic properties of a copolymer and its metal T

complexes: A theoretical and experimental study
Aslisah Acikses, Seda Hekim , Fethiye Oksuz
⁎

Department of Chemistry, Faculty of Science, Firat University, 23119 Elazig, Turkey

Department of Physics, Faculty of Science, Firat University, 23119 Elaziğ, Turkey

ARTICLE INFO ABSTRACT

Keywords: A copolymer containing 4-Diethanolaminomethyl Styrene (DEAMSt) monomer with Benzyl Methacrylate (BMA)
4-Diethanolaminomethyl Styrene monomer units were synthesized by free radical solution polymerization technique using AIBN as a free radical
Benzyl Methacrylate initiator and 1,4-dioxane as a solvent at 60 °C. The metal complexes were prepared by reaction of the copolymer
Hartree-Fock theory used as ligand poly(DEAMSt0.70-co BMA) and Ni(II), Co(II) and Zn(II) metal ions in presence of ethanol and
FT-IR
1 dilute NaOH at 65 °C for 48 h in pH 6. The structure of copolymer used as ligand and polymer-metal complexes
H NMR spectra
HOMO and LUMO energies
were characterized by (FT-IR), 1H NMR, elemental analysis, and SEM-EDX techniques. For the theoretical cal-
culations (FT-IR and 1H NMR spectrum) the Hartree-Fock (HF) theory with 6-31G (6D, 7F) basic set was used. In
addition, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO)
energies were investigated. A good agreement has been found between the theoretical and experimental FT-IR
and 1H NMR results.

1. Introduction 2. Materials and methods

Currently, many researchers have focused on the synthesis of 2.1. Experimental

polymer-metal complexes. Polymer-metal complexes have been a sub-
ject of several theoretical and applied studies, owing to its industrial 2.1.1. The copolymerization of Poly(DEAMSt-co-BMA) used as ligand
importance for many technological applications, such as, nuclear To prepare the copolymer using the free radical polymerization
chemistry, organic synthesis, pollution control, hydrometallurgy, was- method, for this, 0.6786 g (0.0030 mol) of the modified 4-
tewater treatment [1], optics, luminescence, sensor technology [2], Diethanolaminomethyl Styrene (DEAMSt) monomer, 0.5472 g
catalysis, biological and medical [3,4]. In the computational quantum (0.0031 mol) of Benzyl Methacrylate (BMA), 1.4-dioxane (3 mL) as
chemical studies, molecular modeling programs are used to support the solvent, and AIBN (1%) as initiator was placed in the polymerization
results of experimental studies. Quantum theory is the basis of such tube. The prepared polymer tube was passed through argon gas and
computer-aided quantum chemical calculations. These modeling pro- placed in an oil bath at 60 °C and the reaction was continued for 48 h.
grams allow the calculation of all chemical properties of a molecule The resulting copolymer was precipitated with hexane. The precipita-
(molecular structure, total energy, dipole moment, optimized geometry, tion was done three times. The synthesized copolymer was first placed
spectroscopic parameters). In this study, spectroscopic (IR and 1H at room temperature followed by vacuum drying oven at 40 °C for 24 h.
NMR) and electronic properties of synthesized poly(DEAMSt0.70-co- FT-IR, 1H NMR and elemental analysis techniques were used to de-
BMA) ligand and its metal complexes (with Ni(II), Co(II) and Zn(II) termine the structure of the copolymer. The molecular formula of the
metal ions) were investigated using Hartree-Fock [5,6,7](HF) theory. copolymer was determined from elemental analysis results (by using
HF/6-31G (6D, 7F) basic set was used in the calculations and then the values of C, H, N%). The results of the obtained element analysis are
theoretical spectroscopic features were examined and compared with given in Table 1. This synthesized copolymer was used as a ligand in the
some experimental parameters. study. The synthesis reaction was given in Fig. 1. The composition of
the copolymer was found as 70% DEAMSt and 30% BMA (mol), uti-
lizing the aromatic ring protons and N-CH2 protons integral heights in
the 1H NMR spectrum.

⁎
Corresponding author.
E-mail address: [email protected] (S. Hekim).

https://doi.org/10.1016/j.chemphys.2019.110469
Received 13 June 2019; Received in revised form 29 July 2019; Accepted 1 August 2019
Available online 02 August 2019
0301-0104/ © 2019 Elsevier B.V. All rights reserved.
A. Acikses, et al. Chemical Physics 527 (2019) 110469

Table 1
The elemental analysis and SEM / EDX results of poly(DEAMSt0.70-co-BMA) ligand and its metal complexes (Metal; Ni(II), Co(II) and Zn(II)).
Copolymer and It's Metal Complexes Formula Calculated Found SEM/EDX Calculated(M)/Found (M)%
% C: H: N % C: H: N

Poly(DEAMSt0.70-co-BMA) C24H31O4N 72.54: 7.81: 3.53 71.55: 7.97: 3.77 –/–

Poly(DEAMSt0.70-co-BMA)-Ni (C24H29O4N)2-Ni 63.60: 6.84: 3.09 64.27: 7.00: 3.22 12.48 / 12.80
Poly(DEAMSt0.70-co-BMA)-Co (C24H29O4N)2-Co 63.45: 6.83: 3.08 60.08: 6.99: 3.49 12.48 / 12.98
Poly(DEAMSt0.70-co-BMA)-Zn (C24H29O4N)2-Zn 64.56: 6.73: 3.04 67.45: 7.33: 3.26 15.93 / 14.20

CH3
CH3

H2C CH H H2
H2C C H2C C C C
1,4-Dioksan
C O 60 oC 24 h C O

O
O

CH2
CH2
CH2
CH2
N
N

HO OH
HO OH

(a) (b)
Fig. 1. Synthesis reaction of poly(DEAMSt0.70-co-BMA) ligand; a) 4-Diethanolaminomethyl Styrene (DEAMSt); b) Benzyl Methacrylate (BMA).

Fig. 2. The optimized geometry structures of ligand and metal complexes; a) Poly(DEAMSt0.70-co-BMA); b) Poly(DEAMSt0.70-co-BMA)-Ni; c) Poly(DEAMSt0.70-co-
BMA)-Co; d) Poly(DEAMSt0.70-co-BMA)-Zn.

2.1.2. The preparation of copolymer-metal complexes poly(DEAMSt0.70- presence of solvent [1,8] 0,200 g (0,0005 mol) of poly(DEAMSt0.70-co-
co-BMA)-M (M: Ni(II), Co(II) and Zn(II)) BMA) ligand was taken and dissolved in 40 mL ethyl alcohol and was
The metal complexes of the ligand were investigated in relation to placed in a double neck 250 mL flask. The mixture was stirred at 65 °C
Ni(II), Co(II), and Zn(II). From the polymer-metal complexes prepare in for 2 h. Then, the pH of the solution was calibrated by adding dilute

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A. Acikses, et al. Chemical Physics 527 (2019) 110469

Fig. 3. Molecular pioneer orbital representations of the compound according to HF 6-31G (6D,7F) method; (a): Poly(DEAMSt0.70-co-BMA); (b): Poly(DEAMSt0.70-
co-BMA)-Ni; (c): Poly(DEAMSt0.70-co-BMA)-Co; (d): Poly(DEAMSt0.70-co-BMA)-Zn.

0.1 M NaOH solutions in water. After one hour, an aqueous solution of % Ni (II) metal (mol) in the structure of the complex was determined.
0.064 g (0.0003 mol) of Ni (II)acetate (Ni(CH3COO)2·4H2O) was added The results are given in Table 1. The same processes were performed in
dropwise to the mixture. The reaction was refluxed at 65 °C for 48 h. the synthesis of the Co (II) Complex of Poly(DEAMSt0.70-co-BMA) and
The precipitate was filtered and washed with pure water to pH = 6.0 synthesis of Zn(II) Complex of poly(DEAMSt0.70-co-BMA) used as Li-
and dried at 40 °C under a vacuum. The yield of the synthesized metal gand. The yield of the synthesized poly(DEAMSt0.70-co-BMA)-Co metal
complex was calculated as 67%. The color of the metal complex is light complex was 57%. The color of the metal complex is black and the
green, and the product is not soluble in any organic solvent. FT-IR, product is not dissolved in an organic solvent. The yield of the syn-
elemental analysis and SEM / EDX techniques were used to determine thesized Poly(DEAMSt0.70-co-BMA) -Zn metal complex was 57%. The
the structure of the metal complex. Since the poly(DEAMSt0.70-co- color of the metal complex is white and the product is not dissolved in
BMA)-Ni metal complex was not dissolved, the 1H NMR spectrum could an organic solvent. The synthesized copolymer-metal complexes were
not be obtained. The amount of C, H and N% in the structure of the colored and were not solved in any organic solvents because of their
complex by elemental analysis and by with SEM / EDX as the amount of cross-linked nature [9,10]. FT-IR (copolymer used as a ligand and its

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A. Acikses, et al. Chemical Physics 527 (2019) 110469

metal complexes were characterized by Perkin-Elmer Spectrometer FT-

IR by using KBr pellet.), elemental analysis (were taken on a FLASH
2000 (organic) elemental analyzer) and SEM / EDX (metal complexes
were examined on a SU3500 scanning electron microscope (SEM))
techniques were used to determine the structure of the metal com-
plexes. Since the poly(DEAMSt0.70-co-BMA)-Co (II) and Zn (II) metal
complexes did not dissolve, the 1H NMR spectrum (at 400 MHz Bruker
AVENCE III Spectrometer in D6-DMSO using tetramethylsilane (TMS).)
could not be obtained. Also, the 1H NMR spectrum of the copolymer as
used ligand was obtained. The amount of C, H and N% in the structure
of the complex by elemental analysis and by with SEM / EDX as the
amount of Co (II) and Zn (II) metal (mole) in the structure of the
complex was determined. The results are given in Table 1.

2.2. Quantum computational method

Hartree-Fock theory is an ideal method for the determination of

molecular structures, spectroscopic and electronic molecular proper-
ties. Moreover, the availability of this method without the need for any
experimental data increases the interest in this method in recent years.
In this study, HF calculations were carried out by using Gaussian 09 W
[11] software. Geometrical optimization of all structures in the gas
phase was created by using the Hartree-Fock theory at a 6-31G (6D,7F)
Fig. 3. (continued) level of basis set. At the same level of theory and basis set spectroscopic
properties of the title molecule were examined and compared with the
experimental parameters.

3. Results

3.1. Geometric optimization

The approximate geometry of poly(DEAMSt0.70-co-BMA) and Ni

(II), Co(II), Zn(II) complexes of poly(DEAMSt0.70-co-BMA) was ob-
tained in the gas phase using the HF /6-31G (6D, 7F) basis set. The
optimized geometry structures of the molecules are shown in Fig. 2 for
each molecule. The optimized structural parameters are used to cal-
culate vibration frequency at HF levels. No imaginary frequency modes
were obtained in geometries optimized for the header molecule and
derivatives.

3.2. Examination of electronic properties

The formation of chemical reactivity is due to the interaction be-

tween the orbitals of the reactive regions (HOMO and LUMO) [12–15].
The interaction is very easy when the energy difference between the
HOMO-LUMO molecule orbitals is minimal. The main orbitals involved
in chemical reactions are HOMO and LUMO basic orbitals. The elec-
tron-donating ability of the molecule is defined as the HOMO energy,
the ability of the molecule to receive electrons from the LUMO energy.
It is also associated with HOMO-LUMO energy differences with polarity
values of molecules. If the HOMO-LUMO energy differences of a mo-
lecule are small, the electron distribution can be easily steered and the
polarization becomes large, and if the energy differences are large, the
electron distribution will change less, and the polarization will be
lower. Poly(DEAMSt0.70-co-BMA) and Poly(DEAMSt0.70-co-BMA) – Ni
(II), Co (II), Zn (II) derivatives by the HF/6-31G (6D, 7F) method
HOMO-LUMO energies and energy differences values are shown in
Table 3. As seen in Table 3, energy differences are large numbers. This
is indicating that the molecule is thermodynamically stable and dur-
able.
Fig. 4. Experimental (I) and theoretical (II) FT-IR spectra of a) Poly Fig. 3 shows the drawings of HOMO-LUMO orbitals. As shown in the
(DEAMSt0.70-co-BMA) ligand, b) Poly(DEAMSt0.70-co-BMA)-Co, c) Poly figures, the red points are rich in electrons. Furthermore, the location of
(DEAMSt0.70-co-BMA)-Ni and d) Poly(DEAMSt0.70-co-BMA)-Zn Metal the HOMO orbitals also indicates the effectiveness of the molecule.
Complexes. Because chemical reactions take place with HOMO and LUMO orbitals,
the atoms in which the HOMO-LUMO orbitals are located tend to react.

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A. Acikses, et al. Chemical Physics 527 (2019) 110469

Table 2
FT-IR spectra data of poly(DEAMSt0.70-co-BMA) ligand and it's metal complexes.
Copolymer and It's Metal Complexes λ = cm−1

OH –C]O C]C CeN CeO CeOeM

Poly(DEAMSt0.70-co-BMA) 3406 1719 1614 1363, 1250–1152 (s) 1062 (s)

Poly(DEAMSt0.70-co-BMA)- Ni 3416 (b) 1727 1618 1362, 1261–1142)(b) 1069 (b) 1069
Poly(DEAMSt0.70-co-BMA)-Co 3417 (b) 1719 1614 1367, 1250–1152 (b) 1065 (b) 1065
Poly(DEAMSt0.70-co-BMA)-Zn 3440 (b) 1727 1618 1370, 1265–1148 (s) 1066 (b) 1066

S: Strong, b: Broad, C]C: Aromatic Ring Protons, M: Metal ions.

Table 3
HOMO-LUMO energies.
Energy Poly(DEAMSt0.70-co-BMA) Poly(DEAMSt0.70-co-BMA)-Ni(II) Poly(DEAMSt0.70-co-BMA)-Co (II) Poly(DEAMSt0.70-co-BMA)-Zn(II)

EHOMO (eV) −8.168 −7.165 −7.169 −7.321

ELUMO (eV) 3.947 2.986 3.344 3.174
Eg = EHOMO-ELUMO 12.115 10.151 10.513 10.495

co-BMA) ligand and metal complexes are characteristic adsorptions

bands. The FT-IR spectra poly(DEAMSt0.70-co-BMA) ligand has a
characteristic adsorption band for at 3406 cm−1 (–OH) stretching vi-
bration. This band at 3406 cm−1 regions assigned to –OH stretching
vibration of the intramolecular hydrogen band. This band is also ob-
served in the spectra of its metal complexes (Ni(II), Co(II) and Zn(II))
respectively, at 3416, 3417 and 3440 cm−1, but quite shallow and the
high wavenumber peak shifts, demonstrate the formation of metal
complexes. These, depending on the complexes formation have been
increased in peak intensity as a result of interactions between –OH and
metal ions [16]. Consequently, the formation of water inside and out-
side coordination sphere of the metal complexes have been decreased
the bending energy of the –OH band. This is the peak change of –OH
band showed coordination participation with metal ions. The broad
peaks include not only the fraction of the moieties of poly(DEAMSt0.70-
co-BMA) ligand but also complex formation [17]. In the Benzyl Me-
thacrylate (BMA) –C]O stretching vibration at 1719 cm−1 and in the
metal complexes (BMA) –C]O stretching vibration at 1727, 1719 and
1727 cm−1, respectively. The aromatic ring protons C]C stretching
vibration were observed between 1614 and 1618 cm-1and poly
(DEAMSt0.70-co-BMA) the sharp peaks 1363 cm−1 and
−1
1152–1250 cm were referred to the –CeN stretching vibration [18].
These CeN stretching vibration in its metal complexes have been seen
at 1362, 1367 and 1370 cm−1 and 1142–1265 cm−1, respectively. In
the metal complexes CeN peaks have been observed a shift toward high
wavenumber and at 1142–1265 cm−1 have been observed quite
splayed, large and broader peak [19]. In the poly(DEAMSt0.70-co-
BMA) ligand has been appeared CeO strong band at 1062 cm−1, re-
spectively. This band in its metal complexes CeO band have been seen
as quite broader at 1069, 1065 and 1066 cm−1, which demonstrate that
joined in the polymer matrix of the metal ions (CeO in –CeOeNi,
CeO– in –CeOeCo and CeO– in –CeOeZn) [19]. When poly
(DEAMSt0.70-co-BMA) ligand is complexed with the metal because of
the electrical density on the nitrogen it shifts higher wavenumbers. In
the metal complexes (M–O) bands were seen at 460 cm−1, in the lit-
Fig. 5. Experimental and theoretical 1H NMR Spectrum of poly (DEAMSt0.70-
erature appearance M–O bands 550–450 cm−1 [1,19]. The change in
co-BMA) ligand (D6-DMSO).
color of the polymer-metal complexes is due to the orbital transition
which color change results in the change in the energy of orbitals and
3.3. FT-IR and 1H NMR spectra of poly(DEAMSt0.70-co-BMA) ligand and these are possible by binding metal ions. Because these new colors are
its metal complexes not colors neither the metal salt nor the ligand. According to the results
obtained, metal complexes are formed.
The experimental and theoretical structure of poly(DEAMSt0.70-co- Nowadays, Ab initio NMR calculations play an important role in
BMA) ligand and its metal complexes were determined by FT-IR spec- providing accurate information that is useful enough to investigate the
troscopic technique and were showed in Fig. 4(a, b). The FT-IR spectra relationship between chemical shift and molecular structure. It is also a
data of ligand and its metal complexes were given in Table 2. According very useful method for theoretically understanding the relationship
to the data in Table 2, the bonds in the spectrum of poly(DEAMSt0.70- between molecular structure and electronic properties [20,21] 1H and

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A. Acikses, et al. Chemical Physics 527 (2019) 110469

13
C NMR spectroscopy is widely used in the analysis of all organic gap show that the molecule has a stable structure. In addition, the
compounds [21]. In this study, stable molecular geometric structures obtained FT-IR and 1H NMR spectral results were found to be in good
were obtained for 1H NMR chemical shift calculations of poly agreement with the experimental values. It has been suggested that
(DEAMSt0.70-co-BMA) ligand and its metal complexes. In these struc- small shifts between the theoretical and experimental IR and 1H NMR
tures, NMR chemical shift calculations were carried out using the GIAO results are due to the theoretical calculations in the gas phase.
(Gauge- Including Atomic Orbitals) NMR approach using the 6-31G
(6D, 7F) base set in the HF method. References
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