الفهرس 
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Abstract
This thesis includes the study of complexes resulted from the
reaction of (E)-N'-(2-hydroxybenzylidene)-2-phenylacetohydrazide(HL1),
(E)-N'-(1-(2-hydroxyphenyl) ethylidene)-phenylacetohydrazide(HL2) and
(E)-N'-((1-hydroxynaphthalen-2-yl)methylene)-2-phenylacetohydrazide
(HL3) as ligands with Cu(II),Ni(II) and Co(II) metal ion. Acid catalyzed
reaction of HL2 gave a dimer that probably formed via radical mechanism.
The (C=O) group, (C=N) group and phenolic –OH group are the possible
bonding sites in the ligands. The importance of the ligands and their metal
complexes refers to the variety of their application as models in biological,
biochemical, analytical, antimicrobial system, anticancer, antibacterial and
antifungal activities. In this work, the ligands and their metal complexes
were characterized by elemental analysis, spectroscopic studies mass, IR,
1 H NMR, molar conductance, and magnetic moment. Electron spin
resonance (ESR) of [(CuL2) 2 ] and [(CuL3) 2 ] is also curried out. X-ray
crystallography for HL1, HL2, the dimer and [(CuL2) 2 ] is reported. The
spectroscopic characterization of the reported complexes was confirmed by
theoretical studies. Density Functional Theory (DFT) calculations, the
B3LYP/6-311++G** level of theory have been carried out to investigate
the equilibrium geometry of the ligand. The optimized geometry
parameters of the complexes were evaluated using DFT-B3LYP/GENECP
level of theory. Furthermore, the thermogravimetric analysis and Biological
studies including, antimicrobial and antioxidant activities of the complexes
along with fluorescence quenching studies and viscosity measurements are
Summary
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carried out. Also the interaction of the complexes with calf thymus DNA
was studied by different techniques.
This thesis consists of four chapters:
I- Literature Survey,
II- Experimental and Theoretical Background,
III- Results and Discussion.
IIII- biological activity and molecular docking of the ligands and
complexes
Chapter III is divided into four parts;
Part one, Spectroscopic studies and molecular Orbital Calculations of HL1
and its complexes.
Thermal reaction of Cu(CH 3 COO) 2 .H 2 O, Ni(CH 3 COO) 2 .H 2 O and
Co(NO 3 ) 2 with L1 resulted in the formation of [Cu(L1) 2 ].2H 2 O, [Ni(L1) 2 ]
and [Co(L1) 2 ], respectively. X-ray analysis of HL1 confirms the structural
and indicates that the structure is not planer and the molecule as a whole is
unsymmetrical (C 1 system). The elemental analysis and mass spectroscopy
proved that the complexes are structurally formulated in 1:2
[Metal]:[Ligand] ratio. It is confirmed the presence of two hydrated water
molecules in Cu complex. The IR spectrum confirm that M(II) coordinated
to two L1 via three coordinated site oxygen of the phenolic‒OH group,
oxygen of (C=O) group and nitrogen of (C=N) group. Also, indicates the
presence of a water molecule in the Cu complex.
In the complexes,[Cu(L1) 2 ].2H 2 O,[Ni(L1) 2 ] and [Co(L1) 2 ], the metal
ions coordinated to one ligand forming a five‐membered ring,
namely,M44N2N1C47O62 and six-membered ring, namely,
Summary
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M44O39C26C25C24N23, forming octahedral structures. The HOMO-
LUMO and energy gap used in studding the chemical reactivity, softness,
hardness, chemical potential and electro negativity. Natural charge
distribution of the complexes was studied which indicated the electronic
charge distribution in the complexes. The calculated dipole moment and
first order hyperpolarizability results showed that the complexes have a
good non-linear optical behaviour.
Part two, Spectroscopic studies and molecular Orbital calculations of
HL2 and its complexes and the dimer.
Thermal reaction of Cu(CH 3 COO) 2 .H 2 O and Ni(CH 3 COO) 2 .H 2 O with
L2 resulted in the formation of [(Cu L2) 2 ] and [Ni(L2) 2 ],respectively. X-
ray analysis of HL2confirm the structural and showed that it crystallized
with a water molecule, and indicate that the structure of the ligand is not
planer and the molecule as a whole is unsymmetrical (C s system). X-ray
analysis of the dimer confirms the structural and indicates that the molecule
has the symmetry point group S 2 (C 2 + σ v ). The elemental analysis and mass
spectroscopy proved that the Cu complex is structurally formulated in 2:2
[Metal]:[Ligand] ratio, while the Ni complex is structurally formulated in
1:2 [Metal]:[Ligand] ratio. The IR spectrum confirm that the two Cu(II)
coordinated to two L2 via three coordinated site oxygen of the
phenolic‒OH group, oxygen of aromatic -OH group and nitrogen of (C=N)
group. The IR spectrum confirm that Ni(II) coordinated to two L2 via three
coordinated site oxygen of the phenolic‒OH group, oxygen of (C=O) group
and nitrogen of (C=N) group. X-ray analysis of [(CuL2) 2 ] confirm the
structural and indicate that two ligands coordinated as tridentate (two
oxygen and one nitrogen) to form five- and six-membered chelates with
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two Cu ions. It is obvious that the complex has the symmetry point group S 2
(C 2 + σ v ). The copper atom is occurred in a distorted square planar
coordination geometry.
In the two complexes, [(CuL2) 2 ] and [Ni(L2) 2 ], the metal ion
coordinated to one ligand forming a five‐ membered rings, namely,
Cu1N12N11C9O10 for Cu complex and Ni21O9C8N10N11 for Ni
complex and six-membered rings, namely,Cu1O19C15C14C13N12 for Cu
complex and Ni21N11C12C14C19O20 for Ni complex, forming
tetrahedral structure for Cu complex and octahedral structure for Ni
complex. The HOMO-LUMO energy gap used in studding the chemical
reactivity, softness, hardness, chemical potential and electro negativity.
Natural charge distribution of the studied complexes was studied which
indicated the electronic charge distribution in the complexes. The
calculated dipole moment and first order hyperpolarizability results showed
that the complexes have a reasonable good non-linear optical behaviour.
Part three, Spectroscopic studies and molecular Orbital calculations of
HL3 and its complexes and the dimer.
Thermal reaction of Cu(CH 3 COO) 2 .H 2 O, Ni(CH 3 COO) 2 .H 2 O and
Co(NO 3 ) with L3 resulted in the formation of [(CuL3) 2 ], [(NiL3) 2 ]
and[Co(L3) 2 ].2H 2 O.The elemental analysis and mass spectroscopy proved
that the Cu and Ni complex is structurally formulated in 2:2
[Metal]:[Ligand] ratio, while the Co complex is structurally formulated in
1:2 [Metal]:[Ligand] ratio They also confirm the presence of two hydrated
water molecules in Co complex. The IR spectrum confirm that the two
Cu(II) and two Ni(II) coordinated to two L3 via three coordinated site
oxygen of the phenolic‒OH group, oxygen of aromatic -OH group and
Summary
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nitrogen of (C=N) group. The IR spectrum confirm that Co(II) coordinated
to two L3 via three coordinated site oxygen of the phenolic‒OH group,
oxygen of (C=O) group and nitrogen of (C=N) group.
In the complexes,[(CuL3) 2 ],[(NiL3) 2 ] and [Co(L3) 2 ].2H 2 O, the
metal ion coordinated to one ligand forming a five‐ membered rings,
namely,M24N11N10C8O9 and six-membered rings,
namely,M24N11C12C13C18O23, forming tetrahedral structures for Cu
and Ni complexes and octahedral structures for Co complex. The HOMO-
LUMO energy gap used in studding the chemical reactivity, softness,
hardness, chemical potential and electro negativity. Natural charge
distribution of the studied complexes was studied which indicated the
electronic charge distribution in the complexes. The calculated dipole
moment and first order hyperpolarizability results showed that the
complexes have a reasonable good non-linear optical behaviour.
Part four, Electron spin resonance (ESR) of [(CuL2) 2 ] and [(CuL3) 2 ].
The values of g// and g⊥ indicated that Cu(II)-ligand bonds have a
considerable covalent properties, and the unpaired electron is mainly
localized in the d x2‐y2 orbital of the copper(II) ion. The calculated G factors
for the present complexes indicated that there is a significant exchange
interaction between the copper ions.
Chapter IV
(A) Biological activity studies
1- Antimicrobial activity
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The activity of the studied ligands against different microorganisms
is generally enhanced by chelation with the biological active metal. The
complexes of Cu(II) with the three ligands showed the highest biological
activity.
2- Antioxidant activities by DPPH . radical scavenging activity.
The complexes can use as antioxidants; they could facilitate the
scavenging of DPPH . radical. The IC 50 of the complexes follows the order
[(CuL2) 2 ] [(CuL3) 2 ] [Cu(L1) 2 ].2H 2 O [Co(L3) 2 ].2H 2 O [Co(L1) 2 ]
[Ni(L2) 2 ] [Ni(L3) 2 ] [Ni(L1) 2 ].
3- Fluorescence quenching studies.
It was clear that, the addition of the complexes to CT-DNA
pretreated with EB caused a reduction in emission intensity, indicating that
the complexes bind to DNA at the sites occupied by EB. the order of
binding strength follows [(CuL3) 2 ] > [(CuL2) 2 ] > [(NiL3) 2 ] >
[Cu(L1) 2 ].2H 2 O > [Co(L3) 2 ].2H 2 O > [Co(L1) 2 ] > [Ni(L2) 2 ] > [Ni(L1) 2 ].
4- Viscosity measurements.
The result showed an increase in the relative specific viscosity of
DNA (/ o ) 1/3 solution with increasing concentration of complexes. This
indicates that complexes bind to CT-DNA through an intercalation binding
mode. The increased degree of viscosity, which may depend on its affinity
to DNA, follows the order of [(CuL3) 2 ] [(NiL3) 2 ] [(CuL2) 2 ]
[Cu(L1) 2 ].2H 2 O [Co(L3) 2 ].2H 2 O [Co(L1) 2 ] [Ni(L2) 2 ] [Ni(L1) 2 ].
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(B) Molecular docking of the ligands and complexes.
Molecular docking explains the compound-DNA interactions and
the potential binding mode and energy. The docking studies determine the
way by which the docked compounds fundamentally fit in the DNA minor
groove and comprise of hydrophobic, ionic, and hydrogen bonding
interactions with the DNA bases.