Polymer complexes. LXXI. Spectroscopic studies, thermal properties, DNA binding and antimicrobial activity of polymer complexes

Article abstract of DOI:10.1002/aoc.4378

Polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) were prepared by the reaction of 3-allyl-5-[(4-nitrophenylazo)]-2-thioxothiazolidine-4-one (HL) with metal ions. The structure of polymer complexes was characterized by elemental analysis, IR, UV–Vis spectra, X-ray diffraction analysis, magnetic susceptibility, conductivity measurements and thermal analysis. Reaction of HL with Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) ions (acetate or chloride) give polymer complexes (1–5) with general stoichiometric [M(L)(O₂CCH₃)(H₂O)₂]_n (where L?=?anionic of HL and M?=?Co(II) (1) or Ni(II) (2)), [Mn(HL)₂(OCOCH₃)₂]_n (3), [Cr(L)₂(Cl)(H₂O)]_n (4) and [Cd(HL)(O₂CCH₃)₂]_n (5). The value of HOMO–LUMO energy gap (ΔE) for forms (A-C) of monomer (HL) is 2.529, 2.296 and 2.235?eV, respectively. According to ΔE value, compound has minimum ΔE is the more stable, so keto hydrazone form (C) is more stable than the other forms (azo keto form (A), azo enol form (B)). The interaction between HL, polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) with Calf thymus DNA showed hypochromism effect. The HL and its polymer complexes were tested against some bacterial and fungal species. The results showed that the Cr(III) polymer complex (4) has more antibacterial activity than HL and polymer complexes (1–3 and 5) against Bacillus subtilis, Staphylococcus aureus and Salmonella typhimurium.

Full text of DOI:10.1002/aoc.4378

Received: 19 February 2018
DOI: 10.1002/aoc.4378
Revised: 4 March 2018
Accepted: 5 March 2018
F U L L P A P E R
Polymer complexes. LXXI. Spectroscopic studies, thermal
properties, DNA binding and antimicrobial activity of
polymer complexes
M.A. Diab1
| A.Z. El‐Sonbati1
| Sh.M. Morgan2
| M.A. El‐Mogazy1
1 Chemistry Department, Faculty of
Science, Damietta University, Damietta,
Egypt
2 Environmental Monitoring Laboratory,
Ministry of Health, Port Said, Egypt
Polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) were prepared
by the reaction of 3‐allyl‐5‐[(4‐nitrophenylazo)]‐2‐thioxothiazolidine‐4‐one
(HL) with metal ions. The structure of polymer complexes was characterized
by elemental analysis, IR, UV–Vis spectra, X‐ray diffraction analysis, magnetic
susceptibility, conductivity measurements and thermal analysis. Reaction of
HL with Co(II), Ni(II), Mn(II), Cr(III) and Cd(II) ions (acetate or chloride) give
polymer complexes (1–5) with general stoichiometric [M(L)(O2CCH3)(H2O)2]n
(where L = anionic of HL and M = Co(II) (1) or Ni(II) (2)), [Mn(HL)2
(OCOCH3)2]n (3), [Cr(L)2(Cl)(H2O)]n (4) and [Cd(HL)(O2CCH3)2]n (5). The
value of HOMO–LUMO energy gap (ΔE) for forms (A‐C) of monomer (HL)
is 2.529, 2.296 and 2.235 eV, respectively. According to ΔE value, compound
has minimum ΔE is the more stable, so keto hydrazone form (C) is more stable
than the other forms (azo keto form (A), azo enol form (B)). The interaction
between HL, polymer complexes of Co(II), Ni(II), Mn(II), Cr(III) and Cd(II)
with Calf thymus DNA showed hypochromism effect. The HL and its polymer
complexes were tested against some bacterial and fungal species. The results
showed that the Cr(III) polymer complex (4) has more antibacterial activity
than HL and polymer complexes (1–3 and 5) against Bacillus subtilis, Staphylo-
coccus aureus and Salmonella typhimurium.
Correspondence
Sh.M. Morgan, Environmental Monitoring
Laboratory, Ministry of Health, Port Said,
Egypt.
Email: shimaa_mohamad2010@yahoo.
com
KEYWORDS
antimicrobial activity, DNA binding study, polymer complexes, quantum chemical parameters,
thermal analysis
1 | INTRODUCTION
groups due to their biological activities as antitumor,[5]
antibacterial[6] and antifungal.[7] These compounds are
Azo compounds are known for widespread applications
in various fields and have been attention of synthetic
and theoretical chemists. They are the subject of large
research works due to their applications as textile dye,[1]
pharmaceuticals[2,3] and indicators.[4] Azo dyes derived
from heterocyclic amine or derivatives aniline containing
nitrogen in their aromatic rings and their metal com-
plexes have been receiving the attention of research
now in good demands as optical and conducting organic
materials.[8–11] Azo dyes derived from derivatives aniline
moiety and its metal complexes have variety of applica-
tions in biological, analytical and pharmamacological
areas.
A literature survey shows subtle work to synthesis
and characterization of rhodanine azo dyes, also their
metal complexes which widely used in different fields
Appl Organometal Chem. 2018;e4378.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 18
https://doi.org/10.1002/aoc.4378

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DIAB ET AL.
such as biological studies, optical and electrical stud-
ies.[8,9,12] Transition metal polymer complexes of allyl
rhodanine azo compounds are a subject of current and
growing interest and that may have numerous applica-
tions chemically allyl azo rhodanine containing oxygen,
sulphur and nitrogen donor atoms are of great interest
because of their great versatility as ligands,[6,13] due to
presence of several potential donor atoms, their ability
and flexibility to coordinate in either deprotonated or
neutral form.
Cd(CH3COO)2 .2H2O and CrCl3. 6H2O from Sigma
Aldrich.
Organic
solvents
(diethyl
ether,
dimethylformamide (DMF), dimethylsulfoxide (DMSO)
and ethanol) were bought from BDH. The calf thymus
DNA (CT‐DNA) was acquired from SRL (India).
2.2 | Preparation of 3‐allyl‐5‐[(4‐
nitrophenylazo)]‐2‐thioxothiazolidine‐4‐
one (HL) monomer
The reaction of metal ions with polymeric ligands
containing pendant functional groups, which act as che-
lating groups in binding polyvalent metal ions, produces
coordinated systems which possibly have enhanced
thermal stability and thereby improved chemical
resistance.[14]
The present work describes the chelation behavior of
3‐allyl‐5‐[(4‐nitrophenylazo)]‐2‐thioxothiazolidine‐4‐one
(HL) monomer towards to Co(II), Ni(II), Mn(II), Cr(III)
and Cd(II) ions (acetate or chloride). The structure of
the M(II) and Cr(III) polymer complexes is characterized
by elemental analysis, IR, UV–Vis spectra and thermal
analysis. The optimized geometry and quantum chemical
parameters such as highest occupied molecular orbital
energy, the lowest unoccupied molecular orbital energy
and HOMO–LUMO energy gap for HL are discussed.
The antimicrobial activity of HL and its polymer com-
plexes were discussed. The thermodynamic parameters
are calculated using Coats–Redfern and Horowitz–
Metzger methods.
3‐Allyl‐5‐[(4‐nitrophenylazo)]‐2‐thioxothiazolidine‐4‐one
(HL) monomer was synthesized by the well‐established
standard method (Figure 1).[6,13] The resulting solid of
HL was recrystallized with ethanol and then dried in a
vacuum desiccator over anhydrous calcium chloride.
Analytical found for HL monomer (C12H10N4O3S2): C,
44.60; H, 3.00; N, 17.66; S, 20.12% and calculated: C,
44.72; H, 3.11; N, 17.39; S, 19.88%.
IR (KBr, υmax, cm−1): 3391–3255 (N─H str.), 3079
(═C─H str.), 3013 (C─H str. asym.), 2927 (C─H str.
sym.), 1557 (C=C, phenyl ring), 1495 (δNH), 1702
[υ(C=O)], 1604 (‐C=N‐ hydrazone), 1138 (‐N‐N‐), 842
(C=S), 795 (N─H wag).
1H NMR: (DMSO‐d6), δ (ppm): 7.48–8.25 (d, Ar, 4H),
11.64 (NH, hydrazone, exchangeable with D2O), 5.80 (s,
CH2 = CH) for the vinyl CH proton and δ (4.60 (cis),
5.25 (trans)) for the vinyl CH2 protons, these peaks disap-
peared on polymerization.
The mass spectrum of HL shows that the mass of
322 amu related to formula (C12H10N4O3S2) as shown in
Figure S1. It is obvious that, the molecular ion peaks
are in good agreement with their suggested empirical for-
mula as indicated from elemental analysis (Table 1). The
ion of m/z = 322 amu fragmented to stable peak at m/
z = 306 by loss oxygen atom as shown in Scheme 1 (struc-
ture І). The peaks corresponding to various fragments in
HL appeared at m/z = 195 amu (structure ІІ), 149 amu
(structure ІIІ) and 63 amu (structure ІV) by loss
C5H5NS, NO2 and C2H2N2S atoms, respectively.
2 | EXPERIMENTAL
2.1 | Material and reagents
3‐Allyl‐2‐thioxothiazolidin‐4‐one and 4‐nitroaniline were
bought from Aldrich. 2,2′‐Azobisisobutyronitrile (AIBN)
was purified by dissolving in hot ethanol and filtering.
M(CH3COO)2. 4H2O (M = Co(II), Ni(II) and Mn(II)),
FIGURE 1 Tautomeric structures of the
monomer

DIAB ET AL.
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TABLE 1 Elemental analysis of HL and its polymer complexes (1–5)
Exp. (calcd.)%
Compound
C
H
N
S
M
HL
44.60 (44.72)
35.22 (35.37)
34.96 (35.39)
40.94 (41.13)
38.49 (38.53)
34.39 (34.76)
3.00 (3.11)
3.26 (3.37)
3.21 (3.37)
3.21 (3.18)
2.55 (2.68)
2.78 (2.90)
17.66 (17.39)
11.58 (11.79)
11.69 (11.80)
13.59 (13.71)
14.82 (14.98)
10.04 (10.14)
20.12 (19.88)
13.36 (13.48)
13.34 (13.48)
15.45 (15.67)
17.03 (17.12)
11.42 (11.59)
‐
[Co(L)(O2CCH3)(H2O)2]n (1)
[Ni(L)(O2CCH3)(H2O)2]n (2)
[Mn(HL)2(OCOCH3)2]n (3)
[Cr(L)2(Cl)(H2O)]n (4)
[Cd(HL)(O2CCH3)2]n (5)
12.44 (12.41)
12.30 (12.36)
6.66 (6.73)
7.31 (6.96)
20.49 (20.35)
SCHEME 1 The fragmentation
patterns of mass spectrum of HL
increasing the concentration of calf thymus DNA (CT‐
DNA). The intrinsic binding constant (Kb) of the mono-
mer and polymer complexes with calf thymus DNA was
determined.[15,16] The intrinsic binding constant (Kb) of
the HL and its polymer complexes is determined by the
following equation:[15]
2.3 | Preparation of the polymer
complexes
Polymer complexes were prepared by refluxing M(II)
(M = Co(II), Ni(II), Mn(II) and Cd(II) acetate) and Cr(III)
chloride (0.001 mol) with the HL (0.001 mol) in 20 ml
DMF as a solvent, and 0.1% (w/v) AIBN as initiator and
the resulting mixture was heated at reflux for ~ 8 hours.
The hot solution was precipitated by pouring in large
excesses of distilled water containing dilute hydrochloric
acid, to remove the metal ions that were incorporated
into the polymer complexes. The polymer complexes (1–
5, see Table 1) were filtered, washed with water, and
dried in a vacuum oven at 40 °C for several days. All
the polymer complexes are soluble in dimethylformamide
(DMF) and dimethylsulfoxide (DMSO).
½DNAꢀ
½DNAꢀ
1
¼
þ
(1)
ðεa − εf Þ ðεb − εf Þ Kbðεa − εf Þ
where єa is the molar extinction coefficient observed for
the Aobs/[monomer or polymer complex] at the specific
DNA concentration, єf is the molar extinction coefficient
of the free monomer or polymer complex in solution,
[DNA] is the concentration of CT‐DNA in base pairs
and єb is the molar extinction coefficient of the monomer
(HL) or polymer complex when fully bond to DNA.
2.4 | Study the DNA binding
2.5 | Methodology of antimicrobial
activity
The DNA binding study of the monomer and polymer
complexes to Calf thymus DNA (CT‐DNA) was studied
by absorption spectra.[15,16] Electronic absorption spectra
are carried out using 1 cm quartz cuvette at room temper-
ature by fixing the concentration of monomer or polymer
complexes (1 × 10−3 mol L−1), while progressively
The monomer (HL) and its polymer complexes (1–5) of
10 mg/ml concentration were tested for their antibacte-
rial and antifungal activities. The tested compounds were
evaluated against two Gram positive bacteria (Bacillus

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DIAB ET AL.
subtilis and Staphylococcus aureus), two Gram negative
bacteria (Escherichia coli and Salmonella typhimurium)
and two fungal species (Aspergillus fumigatus and
Candida albicans) by diffusion agar technique.[17]
Well diameter (6 mm) was made in the media and
the hole was loaded with the compounds. All compounds
were placed at four equidistant places at a distance of
2 cm from the center in the inoculated Petriplates.
Dimethylsulfoxide (DMSO) was served as control.
Finally, all Petri dishes were incubated at 37 °C and
30 °C after 48 hour and 7 days for bacteria and fungi,
respectively, where inhibition zones were detected around
each disk. Ketoconazole was taken as a reference for the
antifungal effect and Gentamycin was used as standard
for the evaluation of antibacterial activity. All experiments
were performed in triplicate, and data plotted were the
mean value.
The molecular structures of the compounds were opti-
mized by HF method with 3‐21G basis set. The molecules
were built with the Perkin Elmer ChemBio Draw and
optimized using Perkin Elmer ChemBio3D software.[15,16]
Docking calculations were carried out on receptors of
the androgen receptor prostate cancer mutant H874Y
ligand binding domain bound with testosterone and a
TIF2 box3 coactivator peptide 740–753 (PDB code: 2Q7L
Hormone) and crystal structure of the BRCT repeat
region from the breast cancer associated protein, BRCA1
(1JNX Gene regulation).[20–22]
3 | RESULTS AND DISCUSSION
3.1 | Geometrical structure and molecular
docking of HL
Geometrical structure of the keto hydrazone form (C) of
HL is shown in Figure 2. The highest occupied molecular
orbital (HOMO) and lowest unoccupied molecular orbital
(LUMO) for keto hydrazone form (C) of HL is presented
in Figure S2. Quantum chemical parameters of forms
(A‐C) of HL such as HOMO–LUMO energy gap (ΔE),
absolute electro negativities (χ), chemical potentials (Pi),
absolute hardness (η), absolute softness (σ), global soft-
ness (S) and additional electronic charge (ΔNmax) are cal-
culated and given in Table 2 according to the following
equations:[7,15]
2.6 | Analytical measurements
Elemental microanalysis of the separated compounds for
C, H, N and S were analyzed in the Microanalytical Cen-
ter, Cairo University, Egypt. Metal ions were determined
by standard methods.[18] The 1H NMR spectra were
obtained with a JEOL FX90 Fourier transform spectrom-
eter with DMSO‐d6 as the solvent and using
tetramethylsilane (TMS) as an internal standard. The
molar conductance was carried out by Sergeant Welch
Scientific Co., Skokie, IL, USA. The magnetic moment
of the prepared solid complexes was determined at room
temperature using the Gouy's method. Mercury(II)
(tetrathiocyanato)cobalt(II), [Hg{Co(SCN)4}], was used for
ΔE ¼ ELUMO − EHOMO
(2)
(3)
− ðEHOMO þ ELUMO
Þ
χ ¼
2
the calibration of the Gouy tubes. Magnetic moments were
calculated using the equation, μeff. = 2.84[TcM
coor. 1/2
] .
E
LUMO − EHOMO
Diamagnetic corrections were calculated from the
values given by Selwood[19] and Pascal's constants. Mass
spectrum was recorded by the EI technique at 70 eV using
MS‐5988 GS‐MS Hewlett‐Packard. Infrared spectra were
recorded as KBr discs using a Perkin‐Elmer 1340 spectro-
photometer. Ultraviolet–visible spectra of the compounds
were recorded in nujol mulls using a Unicom SP 8800
spectrophotometer. Thermal studies were computed on
Simultaneous Thermal Analyzer (STA) 6000 system using
thermogravimetric analysis (TGA) method. Thermal prop-
erties of the samples were analyzed in the temperature
range from 30 to 800 °C at the heating rate of 10 °C/min
under dynamic nitrogen atmosphere. X‐ray diffraction
analysis of compounds was recorded on X‐ray diffractome-
ter analysis in the range of diffraction angle 2θo = 4–80o.[15]
This analysis was carried out using CuKα radiation. The
applied voltage and the tube current are 40 kV and
30 mA, respectively.
η ¼
(4)
(5)
2
1
σ ¼
η
FIGURE 2 Optimized structure for keto hydrazone form (C) of
HL

DIAB ET AL.
5 of 18
TABLE 2 The quantum chemical parameters for azo keto form (A), azo enol form (B) and keto hydrazone form (C) of HL
Form
EHOMO (eV)
ELUMO (eV)
ΔE (eV)
χ (eV)
η (eV)
σ (eV)−1
Pi (eV)
S (eV)−1
ΔNmax
(A)
(B)
(C)
−5.832
−4.571
−6.635
−3.303
−2.275
−4.400
2.529
2.296
2.235
4.568
3.423
5.518
1.265
1.148
1.118
0.791
0.871
0.895
−4.568
−3.423
−5.518
0.395
0.436
0.447
3.612
2.982
4.937
Molecular docking aims to achieve an optimized
conformation for both the protein and drug with relative
orientation between them such that the free energy of
the overall system is minimized.[3,20–22] In this context,
we used molecular docking between the forms (A‐C) of
HL with the receptors of the prostate cancer (PDB
code: 2Q7L Hormone) and the breast cancer (PDB code:
1JNX Gene regulation). The data showed a favorable
arrangement between the forms (A‐C) of HL and
the receptors of the prostate cancer (PDB code: 2Q7L
Hormone) and the breast cancer (PDB code: 1JNX Gene
regulation) and the interaction curves are shown in
Figures 3–5 and the calculated energy and some parame-
ters with the receptors are listed in Table S2. The HB
plot curves explain the interactions between forms
(A‐C) of HL and receptors (2Q7L and 1JNX) as shown
in Figures S3‐S5. The 2D plot curves of binding for
forms (A‐C) of HL with the receptors (2Q7L and
1JNX) are shown in Figures S6‐S8, appear bending
interaction sites of forms (A‐C) of HL with proteins
active sites of receptors. In general the more value with
negative charge is the most stable interaction, where the
free estimated free energy of binding, the estimated
Pi ¼ − χ
(6)
(7)
1
2η
S ¼
Pi
ΔNmax ¼ −
(8)
η
The reactivity of the azo keto form (A), azo enol form
(B) and keto hydrazone form (C) of HL can be predicted
by considering the minimum HOMO–LUMO energy gap
(ΔE). The value of ΔE for forms (A‐C) of HL is 2.529,
2.296 and 2.235 eV, respectively. According to ΔE value,
compound has minimum ΔE is the more stable, so keto
hydrazone form (C) is more stable than the other forms
(azo keto form (A), azo enol form (B)). The bond lengths
and bond angles for keto hydrazone form (C) of HL are
listed in Table S1. The computed net charges on active
centers for the form (C) of HL are listed in Table 3, it is
found that the most negative charge atoms in HL are
N(1) and O(7) for keto hydrazone form (C) that makes
it react stronger with the metal ion.
TABLE 3 Net charges on active centers for keto hydrazone form (C) of HL
Charges
N(1)
S(2)
N(4)
O(7)
S(8)
N(9)
−0.458
−0.282
−0.420
−0.570
−0.380
−0.442

6 of 18
DIAB ET AL.
2Q7L
(a)
(b)
1JNX
(a)
(b)
FIGURE 3 The monomer (form A) (green in (a) and gray in (b)) in interaction with receptors of 2Q7L and 1JNX
inhibition constant (Ki) and the interact surface area
reveal the most favored binding.[23] So, the obtained
data show a favorable interaction between the forms
(A‐C) of HL and the receptor of 2Q7L (prostate cancer)
than the receptor of 1JNX (breast cancer) (Table S2).
[Mn(HL)2(OCOCH2)2]n (3) and chelates in hydrazone
form as evidence by IR spectra. The magnetic susceptibil-
ity of the polymer complexes (1–4) at room temperature
is in the range of paramagnetic. The polymer complex
[Cd(HL)(O2CCH3)2]n (5) has d10 electronic configuration
and exhibit only intra ligand transition, according to the
empirical formula; an octahedral geometry and diamag-
netic is proposed for this polymer complex.
3.2 | Spectroscopic techniques
The monomer (HL) was synthesized by the direct
diazo coupling reaction between allyl rhodanine and
4‐nitroaniline in 1: 1 molar ratio and the product formed
in high yield and in a physical form suitable for application.
Monomer (HL) can exists in two tautomeric forms, keto
hydrazone form and/or azo enol form. However, the IR
spectra of polymer complexes show intense absorption
band due to the carbonyl stretching of the rhodanine
moiety. This confirms that the keto hydrazone form is
bonded to the metal in the solution. The polymer
complexes [M(L)(O2CCH3)(H2O)2]n, [M = Co(II) (1),
Ni(II) (2)], [Mn(HL)2(OCOCH2)2]n (3) and [Cr(L)2(Cl)
(H2O)]n (4) were readily formed by the reaction of the
monomer with corresponding metal ions. The monomer
undergoes deprotonation to L except polymer complex
The elemental analysis, stoichiometries of HL and
its polymer complexes are presented in Table 1. The
molar conductivities (ΛM) values of these metal polymer
complexes are in the range of 10.8–19.5 Ω−1 cm2 mol−1 at
room temperature, indicating their almost non‐electrolytic
nature. These low values indicate that metal polymer
complexes are non‐electrolytes due to lack of counter
ions in the proposed structures of the metal polymer
complexes (Figure S9). The difference in the number
of protons in the metal polymer complexes probably
points the difference in the sizes of the oxidation state
of these metal ions, with the different polarizing due to
its different sizes.
The electronic spectrum of the monomer (HL),
showed many bands at 37040 cm−1 and 30860 cm−1
,

DIAB ET AL.
7 of 18
2Q7L
(a)
(b)
1JNX
(a)
(b)
FIGURE 4 The monomer (form B) (green in (a) and gray in (b)) in interaction with receptors of 2Q7L and 1JNX
assigned to π → π* (intra‐ligand of aromatic system,
C=C) and n → π* transitions within the molecule
(C=O), respectively.[24] C=S group merge to form a
single strong absorption band ~ 30860 cm−1. Most bands
were slightly shifted in all the polymer complexes indicat-
ing coordination of the monomer to the metal. The band
~ 22250 cm−1 is characteristic for the ligand to metal
charge transfer (LMCT) from the nitrogen atom to the
transition metal center.
15210 cm−1 (4T1g
→
4A2g) (υ2) and 18700 cm−1
(4T1g(F) → T1g(P)) (υ3), suggesting that there is an
octahedral geometry around Co(II) ion.[6] Various ligand
field parameters for the polymer complex were calculated
and listed in Table 4. The nephelauxetic parameter (β)
indicates appreciable covalent character in this polymer
complex. The spectral parameters υ2/υ1, 10Dq, B and β
were calculated and agreed well with the reported values
for octahedral structure.
4
3.2.1 | Cobalt(II) polymer complex
3.2.2 | Nickel(II) polymer complex
The room temperature magnetic moment of the
cobalt(II) polymer complex (5.05 B.M.) is characteristic
of high‐spin octahedral Co(II) polymer complex.[6,15]
IR spectrum of cobalt(II) polymer complex shows
that the acetate group coordinate to Co(II) ion in a
bidentate manner where the difference between the
asymmetric and symmetric stretching vibrations of the
The Ni(II) polymer complex is paramagnetic and shows
an effective magnetic moment of 2.80 B.M., which is
within the range expected for two unpaired electron.[25]
Its electronic spectrum shows three bands at
~ 10520 cm−1 (3A2g
→
3T2g(F)) (υ1), 19995 cm−1
3
3
(3A2g → T1g(F)) (υ2) and 24990 cm−1 (3A2g → T1g(P))
(υ3) transition, and this are suggestive of octahedral
geometry around the nickel(II) ion.[26] A small contribu-
tion because of spin‐orbit coupling between the first
acetate group is Δυ ≤ 180 cm−1 [7]
trum shows bands at 9620 cm−1 (4T1g → T2g(F)) (υ1),
.
The electronic spec-
4

8 of 18
DIAB ET AL.
2Q7L
(a)
(b)
1JNX
(a)
(b)
FIGURE 5 The monomer (form C) (green in (a) and gray in (b)) in interaction with receptors of 2Q7L and 1JNX
TABLE 4 Ligand field parameters of the polymer complexes
Complexa
υ2/υ1
10Dq (cm−1
)
B (cm−1
)
β
βo (%)
(1)
(2)
(3)
(4)
1.58
1.90
1.18
1.42
8520
532
895
832
425
0.48
0.86
0.95
0.46
52
14
5
10520
18340
18580
54
aNumbers as given in Table 1.
3
3
excited state T2g and the ground state A2g leads to a
magnetic moment above the spin only value.[27] The
asymmetric and symmetric stretching vibrations of the
acetate group appear at 1520 and 1384 cm−1, respectively,
for the nickel(II) acetate having the separation value
Δυ = 136 cm−1 suggests the presence of bidentate chelat-
ing acetate group linked with Ni(II) ion center.[12]
of three unpaired electrons. The presence of coordinated
water molecule in the polymer complex is indicated by
broad band at ~ 3500 cm−1 and two weaker bands in
~ 780 and 705 cm−1 due to υ(‐OH) rocking and wagging
mode of vibrations, respectively. Irrespective of the strength
of the ligand field, three will be three unpaired electrons
in binuclear Cr(III) polymer complex. The electronic spec-
trum of Cr(III) polymer complex exhibits three bands at
~ 18580 cm−1 (4A2g → 4T2g), 24910 cm−1 (4A2g → 4T1g (F))
and charge‐transfer. From the electronic spectrum, it is
concluded that Cr(III) polymer complex may have an
octahedral geometry.[28] Various ligand field parameters
are calculated and given in Table 4. Dq value has been
3.2.3 | Chromium(III) polymer complex
Chromium(III) polymer complex shows magnetic moment
in the 3.89 B.M., which is in agreement with the presence

DIAB ET AL.
9 of 18
evaluated by using Orgal energy level diagram. The
nephelauxetic parameter (β) is obtained by using the rela-
tion: β = B (complex)/B (free ion). The β value indicates
that the polymer complex has appreciable covalent
character.
coordination of nitrogen of hydrazone group. This has
been confirmed by the bands in the 435–450 cm−1 range
and it is assignable to the υ(M‐N) band.[6] The presence
of bands in the range of 1597–1594 cm−1 in polymer com-
plexes due to asymmetric stretching vibration of the
newly formed C=N‐ bond demonstrates the hydrazone
structure of the monomer. The two intense carbonyl
bands [υ(C=O…H), υ(C=O)] of the monomer at
1702 cm−1 undergoes a negative shift of wavenumber in
the polymer complexes indicating coordination via
carbonyl oxygen. This has been confirmed by the bands
in the 560–575 cm−1 range and it is assigned to the
υ(M‐O).[7] In Co(II) and Ni(II) polymer complexes
(1 and 2), the bands of coordinated water observed at ~
854 and ~ 745 cm−1, are assigned to ρr(H2O) and
ρw(H2O), respectively. Moreover, strong evidence for the
presence or absence of water of crystallization and/or
coordinated water supported by the thermograme of all
the polymer complexes. In Mn(II) polymer complex (3),
the C=O and NH of hydrazone, stretching frequency
bands observed at 1702 and 3391–3255 cm−1 for the
free monomer and shifted to lower frequencies (~ 1676
and 3382 cm−1) in polymer complex. This is due to the
modification of hydrogen bonding interaction upon com-
plex formation. The new additional bands observed with
the difference Δυ = 243 cm−1 confirms the monodentate
nature of the coordinated two acetate groups.[16]
3.2.4 | Manganese(II) polymer complex
The magnetic moment of the manganese(II) polymer
complex at room temperature is 5.95 B.M., corresponding
to five unpaired electrons. The electronic spectrum
4
exhibits three bands at 22285 cm−1 (6A1g → A1g (G),
4Eg (G)) (υ3), 21645 cm−1 (6A1g
→
4T2g (G)) (υ2) and
18340 cm−1 (6A1g → T1g (G)) (υ1) transition, inside an
octahedral configuration. Values of 10Dq, Racah (B) and
nephelauxetic parameters (18340 cm−1, 832 cm−1 and
0.95) are calculated and indicate ionic character. The
magnitude of Δυ = υas (COO−) – υsym(COO−) = 243 cm−1
suggest the coordination of acetate group in the
monodentate fashion.[16]
4
Various ligand parameters were calculated for the
polymer complexes are listed in the Table 4. The value
of β indicates the appreciable covalent character of metal
sigma “σ” bond. The effect of covalence is to reduce the
positive charge on the metal ion as a consequence of
inductive effect to the ligand with reduced positive
charge, the radial extension of the d‐orbital increases.
By tracing the IR spectrum of uncomplexed azo, no
υNH2 of aniline stretching vibration is apparent.[29] This
supports the formation of azo monomer. The mode of
bonding of the HL to the metal ions was elucidated by
comparing the IR spectra of the polymer complexes with
literature data for related systems.
The IR spectrum of monomer shows bands in
the range of 3391–3255 cm−1 due to asymmetric and
symmetric stretching vibrations of NH (hydrazone)
group and intramolecular hydrogen bonding N‐H…O
systems (Figure 1). A strong band at ~ 1604 cm−1 can
guide to assume the presence of C=N‐ of hydrazone
structure through resonating phenomena.[6,30–32] In the
IR spectrum, υ(‐C=N‐NH, hydrazone) band of monomer
disappear in polymer complexes (1, 2 and 4) but
appear in polymer complex [Mn(HL)2(OCOCH3)2]n (3)
(3382 cm−1 due to –C=N‐NH), also adding more evidence
for the hydrazone and deprotonation of the hydrazone
proton (C=N‐N‐) prior to coordination of nitrogen to
the metal ion and it is supported to a great extent by
the appearance of a new peak due to υ(M‐N) stretching
frequency. A strong band found at 1138 cm−1 is assigned
to the υ(N‐N) band of the monomer. The positive
shift of the frequency assigned to υ(N‐N) band in the
spectra of polymer complexes is owing to the
The 1H NMR spectrum of HL supports the
occurrence of the form depicted in Figure S10. The
proton NMR spectra of the HL monomer and Cd(II)
polymer complex (5) were recorded in DMSO‐d6 using
tetramethylsilane (TMS) as the internal standard
(Figure S10(a) and S11(a)). The protons of the aro-
matic ring resonate downfield in the range 7.48–8.25
(4H) and 7.30–8.15 ppm for HL and Cd(II) polymer
complex (5), respectively. The broad signal at
11.40 ppm was assigned to intramolecular hydrogen
bonded proton of NH (hydrazone) (Figure 1) which
disappeared in the presence of D2O (Figure S10(b)).
The proton of NH (hydrazone) of HL and Cd(II)
polymer complex (5) showed a signal at 11.64 ppm
and 9.90 ppm, respectively. The shift of the proton of
NH Cd(II) polymer complex (5) is due to the coordination
of the nitrogen atom of NH (hydrazone) group with
Cd(II) ion. The last two protons disappear in the presence
of D2O as shown in Figures S10(b) and S11(b). Absence
of –CH proton signal of rhodanine moiety and a new
C=N‐NH signal appear upon complexation, indicated
the existence of the monomer in the keto hydrazone
form. The 1H NMR spectrum of HL showed the expected
peaks and pattern of the vinyl group (CH2═CH), i.e.
5.80 ppm for the vinyl CH proton and 4.60 ppm (cis)
and 5.25 ppm (trans) for the vinyl CH2 protons; these

10 of 18
DIAB ET AL.
peaks disappeared on polymerization. This indicates
that the polymerization of HL occurs at the vinyl group.[6]
It is worth noting that the rest of the proton spectrum
of HL remains almost without change. On the basis of
all the above spectral data, an internally hydrogen
bonded keto hydrazone structure has been proposed for
the monomer (Figure 1).
3.3 | X‐ray diffraction analysis
Single crystals of HL and its polymer complexes (1–5)
could not be prepared to get the X‐ray diffraction (XRD)
and hence the powder diffraction data were obtained for
structural characterization. Structure determination by
X‐ray powder diffraction data has gone through a recent
FIGURE 6 X‐ray diffraction patterns of HL and its polymer complexes (1–5)

DIAB ET AL.
11 of 18
surge since it has become important to get to the struc-
tural information of materials, which do not yield good
quality single crystals.
The X‐ray diffraction analysis (XRD) patterns of
HL and its polymer complexes (1–5) are shown in
Figure 6. The XRD pattern of HL shows many diffraction
peaks confirm the polycrystalline phase. The XRD pat-
terns of polymer complexes (1–5) show in the range of
2θo = 20 ‐ 28o a broad peak indicating a completely
amorphous nature for these polymer complexes.[6]
The experiment was performed in temperature range from
30 to 800 °C at heating rate of 10 °C/min under dynamic
nitrogen atmosphere. The thermogravimetric curves of
polymer complexes (1–5) are shown in Figure 7. It
was found that the thermal behaviors of the two polymer
complexes (1) and (2) are similar. A three steps weight
losing processes were involved in this experiment. The
thermogravimetric analysis curves of HL and its polymer
complexes (1–5) are shown in Figure 7 and loss of mass
listed in Table 5.
The TG curve of the HL showed three steps of
decomposition. The first step in the temperature range
125–313 °C attributed to loss of C6H5NO2 (found
37.95%; calcd. 38.20%) and the second step in temperature
range 313–764 °C attributed to loss of C2HN3OS
3.4 | Thermogravimetric analysis
The thermal decomposition of HL and its polymer
complexes (1–5) was studied using the TG‐technique.
FIGURE 7 TGA curves of HL and its polymer complexes (1–5)

12 of 18
DIAB ET AL.
TABLE 5 Thermogravimetric analysis results of HL and its polymer complexes
Temp.
Found mass
Total mass loss Residue Found
Found (calcd.) % (calcd.) %
Compounda range (°C) loss (calcd.) % Assignment
HL
(1)
125–313
313–764
> 764
37.95 (38.20)
35.66 (35.71)
26.39 (26.09)
Loss of C6H5NO2
Loss of C2HN3OS
Loss of C4H4S
100 (100)
‐
50–134
7.53 (7.58)
Loss of two water molecules in inside of the
coordination sphere.
74.05 (74.12)
CoO + 4 Carbon
atoms
134–390
390–800
30.66 (30.74)
35.86 (35.80)
Loss of acetate group and C3H5NS
Loss of C5H4N3O2S
25.95 (25.88)
(2)
80–235
20.16 (20.01)
Loss of two water molecules in inside of the
coordination sphere and acetate group.
Loss of C3H5NS
71.78 (71.63)
NiO + 5 Carbon
atoms
28.22 (28.37)
235–438
438–800
18.40 (18.33)
33.22 (33.29)
Loss of C4H4N3O2S
(3)
(4)
140–278
278–462
462–800
24.33 (24.48)
11.38 (11.26)
52.49 (52.64)
Loss of two acetate groups and C6H10
Loss of N2O4
Loss of C16H10N6OS4
88.20 (88.38)
89.32 (89.83)
MnO + 2
Carbon atoms
11.80 (11.62)
150–280
33.70 (34.18)
Loss of one water molecule in inside of the
coordination sphere and C6H10N4O4Cl
Loss of C2S4
½Cr2O3
10.68 (10.17)
280–430
430–800
20.54 (20.33)
35.08 (35.32)
Loss of C16H8N4O0.5
(5)
50–280
280–595
595–800
33.13 (34.21)
12.79 (12.67)
21.66 (21.18)
Loss of two acetate groups and C3H5NO
Loss of C2NS
Loss of C3H5N2OS
67.58 (68.06)
CdO + 4 Carbon
atoms
32.42 (31.94)
aNumbers as given in Table 1.
(found 35.66%; calcd. 35.71%). Third step represented the
loss of C4H4S at >764 °C (mass loss: found 26.39%, calcd.
26.09%).
The Mn(II) polymer complex (3) began decomposing
at 140 °C in three decomposition steps. The first
step of decomposition found within the temperature
range of 140–278 °C corresponded to loss of two acetate
groups and C6H10. It represented weight loss of 24.33%,
which is in good agreement with the calculated value
of 24.48%. The second step of decomposition found
within the temperature range of 278–462 °C which
was assigned to loss of N2O4. It represented a weight
loss of 11.38% which is in good agreement with the
calculated value of 11.26%. The third step of decomposi-
tion found within the temperature range of 462–800 °C
which was assigned to loss of C16H10N6OS4. It repre-
sented a weight loss of 52.49% which is in good
agreement with the calculated value of 52.64%. The
decomposition of this polymer complex ended with
leaving MnO and two carbon atoms residue with mass
percent of 11.80% (calcd. 11.62%).
Cr(III) polymer complex (4) was thermally stable up
to 150 °C. Decomposition of the polymer complex began
at 150 °C to 800 °C. The thermal decomposition of this
polymer occurred completely in three steps. The first
decomposition step within the temperature range 150–
280 °C corresponded to the loss of coordinated water mol-
ecule and C6H10N4O4Cl with a mass loss of 33.70% (calcd.
34.18%) and the second decomposition step at 280–430 °C
For Co(II) polymer complex (1), according to Figure 7,
the first weight loss of 7.53% corresponding to the loss of
two water molecules in inside of the coordination sphere
(calcd. 7.58%) occurred in temperature range 50–134 °C.
The second weight loss of 30.66% corresponding to the loss
of acetate group and C3H5NS (calcd. 30.74%) occurred in
the range of 134–390 °C. The third weight loss of 35.86%
corresponding to the loss of C5H4N3O2S (calcd. 35.80%)
occurred in the range of 390–800 °C. CoO and four carbon
atoms is a residue with mass percent of 25.95% (calcd.
25.88%).
The thermogram of Ni(II) polymer complex (2) showed
three decomposition steps. The first decomposition step
within the temperature range 80–235 °C corresponded to
the loss of two water molecules in inside of the coordina-
tion sphere and acetate group with a mass loss of 20.16%
(calcd. 20.01%) and the second decomposition step at
235–438 °C which related to loss of C3H5NS (found
18.40%; calcd. 18.33%). The third step in the temperature
range of 438–800 °C corresponded to the loss of C4H4N3O2S
with a mass loss of 33.22% (calcd. 33.29%) and leaved NiO
and five carbon atoms as a residue with mass percent of
28.22% (calcd. 28.37%).

DIAB ET AL.
13 of 18
which related to loss of C2S4 (found 20.54%; calcd.
20.33%). The third decomposition step within the temper-
ature range of 430–800 °C corresponded to the loss of
C16H8N4O0.5 with a mass loss of 35.08% (calcd. 35.32%)
and leaved ½Cr2O3 as a residue with mass percent of
10.68% (calcd. 10.17%).
The thermal analysis curve of Cd(II) polymer
complex (5) indicated that decomposition took place
in three decomposition steps. The first and second
steps of decomposition within the temperature range
of 50–280 °C and 280–595 °C, have weight loss about
33.13% (calcd. 34.21%) and 12.79% (calcd. 12.67%), and
was attributed to the loss of two acetate groups,
C3H5NO and C2NS, respectively. Third step represented
the loss of C3H5N2OS at 595–800 °C (mass loss: found
21.66%, calcd. 21.18%) to give finally CdO and four car-
bon atoms as a residue with mass percent of 32.42%
(calcd. 31.94%).
decomposition (Ea), enthalpy (ΔH*), Gibbs free energy
change of the decomposition (ΔG*) and entropy (ΔS*)
are calculated by Coast‐Redfern and Horowitz‐Metzger
methods.[33,34] The enthalpy (ΔH*) and Gibbs free
energy of decomposition (ΔG*) were calculated by
ΔH* = Ea − RT and ΔG* = ΔH* − TΔS*, respectively.
The thermodynamics parameters obtained with the
Coast‐Redfern and Horowitz‐Metzger methods for of
HL and its polymer complexes (1–5) are listed in
Table 6 (Figures 8 and 9). The thermodynamics param-
eters data obtained from the two methods of Coast‐
Redfern and Horowitz‐Metzger methods are compara-
ble and can be considered in good agreement with
each other.[35,36] The data obtained are summarized in
the following:
1. The values of ΔG* for HL and its polymer complexes
are positive values and confirmed the process is non‐
spontaneous.
2. The values of ΔS* for HL and its polymer complexes
are negative values indicate the reaction is slow or
more ordered activated polymer complex than the
reactants.[12,36]
3.5 | Kinetic studies
The thermodynamics parameters of HL and its polymer
complexes (1–5) as the thermal activation energy of
TABLE 6 Thermodynamic data of the thermal decomposition of HL and its polymer complexes
Thermodynamic parameters
Decomposition
Correlation
ΔG* (kJ mol−1
) coefficient
Compounda
temperature (oC) Method Ea (kJ mol−1
)
ΔS* (J mol‐1 K‐1
)
ΔH* (kJ mol−1
)
HL
185‐307
307‐490
CR
HM
CR
119
120
52.2
63.0
‐73.2
‐57.1
‐224
‐207
115
116
46.7
57.4
153
146
197
196
0.98975
0.99572
0.99364
0.99223
HM
(1)
(2)
(3)
(4)
(5)
50‐395
CR
HM
CR
21.3
24.7
106
110
‐267
‐251
‐181
‐153
17.2
20.6
99.5
104
149
145
236
219
0.98744
0.99345
0.99623
0.99254
395‐565
HM
95‐402
CR
HM
CR
30.7
38.2
153
145
‐248
‐225
‐108
‐102
26.3
33.9
147
139
156
151
227
215
0.99313
0.99339
0.99004
0.99664
402‐545
HM
140‐278
278‐462
CR
HM
CR
52.5
60.2
46.8
56.8
‐190
‐168
‐231
‐212
48.5
56.2
41.5
51.4
140
137
190
188
0.98724
0.98889
0.98918
0.99095
HM
155‐280
280‐430
CR
HM
CR
83.8
93.0
59.7
68.0
‐117
‐100
‐206
‐190
79.7
88.9
54.4
62.8
137
138
184
182
0.99256
0.99850
0.99093
0.99085
HM
130‐280
280‐595
CR
HM
CR
65.1
74.4
26.0
29.2
‐148
‐135
‐281
‐267
61.1
70.4
20.1
23.3
132
135
220
213
0.99329
0.9965
0.98702
0.99086
HM
aNumbers as given in Table 1.

14 of 18
DIAB ET AL.
FIGURE 8 Coats–Redfern (CR) of HL and its polymer complexes (1–5)
3. The value of the thermal activation energy of
decomposition (Ea) for the HL is the highest than
the polymer complexes.
4. The Ea value of Ni(II) polymer complex (2) is higher
than the Ea value of Co(II) polymer complex (1).[15]
information and instructs the biological synthesis.[7,35,37]
The intercalation of HL and its polymer complexes with
Calf thymus DNA (CT‐DNA) is carried out using
absorption spectroscopy to determine the intrinsic bind-
ing constant (Kb) to CT‐DNA. In presence of DNA, the
absorption bands of the HL and its polymer complexes
(1–5) exhibited hypochromism and red shift of about
1–4 nm at about 433, 414, 420, 345, 431 and 430 nm
for HL and its polymer complexes (1–5), respectively,
(Figure S12). It was found that the absorption bands
of the HL and its polymer complexes decrease with
3.6 | DNA binding study
DNA is one of the most important biomacromolecules
in life processes because it carries inheritance

DIAB ET AL.
15 of 18
FIGURE 9 Horowitz‐Metzger (HM) of HL and its polymer complexes (1–5)
increasing concentration of CT‐DNA.[12] In plots of
[DNA]/(єa–єf) versus [DNA] (Figure S12) were deter-
mined intrinsic binding constants (Kb). The value of
intrinsic binding constant (Kb) of HL with CT‐DNA
was determined and it was found that the complexation
lead to increases of the Kb value than HL free.
The values of intrinsic binding constant (Kb) for
HL and its polymer complexes (1–5) are calculated
and found to be 1.80 × 104, 8.16 × 104, 9.89 × 104,
3.37 × 104, 2.62 × 105 and 1.57 × 105, respectively.
From the values of intrinsic binding constant (Kb) show
Ni(II) polymer complex (2) has high value of Kb with com-
pared to Co(II) polymer complex (1) may be due to the
lower ionic radius of Ni(II) with compared to Co(II).[15]
Also it was found that the Cr(III) polymer complex (4) is
the highest value of Kb than HL and polymer complexes
(1–3 and 5), this indicated that the Cr(III) polymer complex
(4) is highly binding with CT‐DNA. The polymer com-
plexes revealed higher efficient binding to DNA than HL
monomer and these varieties in Kb values of polymer com-
plexes are mainly due to the effect of the type of metal and
the coordinated sphere groups (acetate or chloride).

16 of 18
DIAB ET AL.
than HL and polymer complexes (1–3 and 5) against
Bacillus subtilis, Staphylococcus aureus and Salmonella
typhimurium. There are six factors that govern the biolog-
ical activity of the metal complexes: (i) the nature of the
donor atoms, (ii) the chelate effect of the monomer, (iii)
the nature of the metal ion, (iv) the total charge on the
complex ion, (v) the geometrical structure of the
complex and (vi) the nature of the counter ions that
neutralize the complex.[35,38]
The results of the antifungal activity of the HL and
polymer complexes (1–5) are listed in Table 8. HL and
polymer complexes (1–3) have no antifungal activity
against Aspergillus fumigatus and Candida albicans but
Cr(III) and Cd(II) polymer complexes (4 and 5) have
effects against Aspergillus fumigatus and Candida
albicans.
3.7 | Antimicrobial activities study
Antifungal and antibacterial activities of HL and polymer
complexes (1–5) were examined and the data were
recorded in Tables 7 and 8. HL has antibacterial activity
against Bacillus subtilis and Staphylococcus aureus and
the inhibition zone was 17 and 15 mm, respectively, and
has antibacterial activity against Escherichia coli and Sal-
monella typhimurium and the inhibition zone was 18 and
17 mm, respectively.
Co(II) polymer complex (1) and Mn(II) polymer
complex (3) have no antibacterial activity against Bacillus
subtilis, Staphylococcus aureus, Escherichia coli and Sal-
monella typhimurium. Ni(II) polymer complex (2) has
no antibacterial activity against Bacillus subtilis and
Staphylococcus aureus but has antibacterial activity
against Escherichia coli and Salmonella typhimurium
and the inhibition zone was 12 and 11 mm, respectively.
Cr(III) polymer complex (4) has antibacterial activity
against Bacillus subtilis and Staphylococcus aureus and
the inhibition zone was 20 and 21 mm, respectively, as
well as has antibacterial activity against Escherichia coli
and Salmonella typhimurium and the inhibition zone
was 15 and 21 mm, respectively. It was found that Cr(III)
polymer complex (4) is more antibacterial activity than
the Gentamycin (standard of antibacterial drug) against
Salmonella typhimurium. The activity of the Cr(III) poly-
mer complex (4) may be because of there are one chlo-
ride ion, type of the metal and 1:2 molar ratio.[38] Cd(II)
polymer complex (5) has antibacterial activity against
Bacillus subtilis and Staphylococcus aureus and the inhibi-
tion zone was 15 and 16 mm, respectively, as well as has
antibacterial activity against Escherichia coli and Salmo-
nella typhimurium and the inhibition zone was 14 and
15 mm, respectively.
From a comparative study of the growth inhibition zone
values of antifungal activity for HL and polymer complexes
(1–5), it is found that the Cr(III) and Cd(II) polymer com-
plexes (4 and 5) have higher activity than the HL against
TABLE 8 Antifungal activity data of HL and its metal polymer
complexes (1–5). The results are recorded as the diameter of inhi-
bition zone (mm)
Aspergillus
fumigatus
Candida
albicans
Compounda
HL
(1)
(2)
(3)
(4)
(5)
‐ve
‐ve
‐ve
‐ve
20
‐ve
‐ve
‐ve
‐ve
10
22
11
Ketoconazole (Standard of
antifungal drug)
17
20
From these results it was found that the Cr(III)
polymer complex (4) is more antibacterial activity
aNumbers given in Table 1.
TABLE 7 Antibacterial activity data of HL and its metal polymer complexes (1–5). The results are recorded as the diameter of inhibition
zone (mm)
Gram positive bacteria
Gram negative bacteria
Compounda
Bacillus subtilis Staphylococcus aureus Escherichia coli Salmonella typhimurium
HL
(1)
(2)
(3)
(4)
(5)
17
15
18
‐ve
12
‐ve
15
14
30
17
‐ve
11
‐ve
21
15
17
‐ve
‐ve
‐ve
20
‐ve
‐ve
‐ve
21
15
16
Gentamycin (Standard of antibacterial drug) 26
aNumbers given in Table 1.
24

DIAB ET AL.
17 of 18
[8] N. A. El‐Ghamaz, A. Z. El‐Sonbati, Sh. M. Morgan, J. Mol.
Struc. 2012, 1027, 92.
Aspergillus fumigatus and Candida albicans as shown in
Table 8. Our results are similar to Habib et al.[39] who stud-
ied the antimicrobial activities of some rhodanine deriva-
tives and they revealed that the most pronounced activity
was the antifungal activity against Aspergillus niger.
[9] Sh. M. Morgan, N. A. El‐Ghamaz, M. A. Diab, J. Mol. Struct.
2018, 1160, 227.
[10] N. A. El‐Ghamaz, M. A. Diab, A. Z. El‐Sonbati, Sh. M. Morgan,
O. L. Salem, Chem. Pap. 2017, 71, 2417.
[11] (a) N. A. El‐Ghamaz, A. Z. El‐Sonbati, M. A. Diab, A. A. El‐
Bindary, Sh. M. Morgan, Mater. Res. Bull. 2015, 65, 293. (b) N.
A. El‐Ghamaz, A. Z. El‐Sonbati, M. A. Diab, A. A. El‐Bindary,
G. G. Mohamed, Sh. M. Morgan, Spectrochim. Acta A 2015,
147, 200. (c) N. A. El‐Ghamaz, A. Z. El‐Sonbati, M. A. Diab,
A. A. El‐Bindary, M. K. Awad, Sh. M. Morgan, Mater. Sci.
Semicond. Proc. 2014, 19, 150.
4 | CONCLUSION
3‐Allyl‐5‐[(4‐nitrophenylazo)]‐2‐thioxothiazolidine‐4‐one
(HL) and its Co(II), Ni(II), Mn(II), Cr(III) and Cd(II)
polymer complexes were prepared and characterized by
elemental analysis, IR spectra and thermal analysis. The
X‐ray diffraction analysis (XRD) pattern of HL shows
many diffraction peaks confirm the polycrystalline phase.
The values of intrinsic binding constant (Kb) for HL and
its polymer complexes (1–5) are calculated and it was
found that the Cr(III) polymer complex (4) is the highest
value of Kb than HL and polymer complexes (1–3 and 5),
this indicated that the Cr(III) polymer complex (4) is
highly binding with CT‐DNA. The value of the thermal
activation energy of decomposition (Ea) for the HL is
the highest than the polymer complexes. Cr(III) polymer
complex (4) has more antibacterial activity than HL and
polymer complexes (1–3 and 5) against Bacillus subtilis,
Staphylococcus aureus and Salmonella typhimurium. As
well as Cr(III) and Cd(II) polymer complexes (4 and 5)
have effects against Aspergillus fumigatus and Candida
albicans.
[12] A. Z. El‐Sonbati, M. A. Diab, Sh. M. Morgan, J. Mol. Liq. 2017,
225, 195.
[13] M. A. Diab, A. Z. El‐Sonbati, A. A. El‐Bindary, M. Z. Balboula,
J. Mol. Struc. 2013, 1040, 171.
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M.A. Diab http://orcid.org/0000-0002-9042-1356
A.Z. El‐Sonbati http://orcid.org/0000-0001-7059-966X
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How to cite this article: Diab MA, El‐Sonbati
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