Research of Phthalocyanines

1.0.
INTRODUCTION
1.1. Phthalocyanines
The past two decades have seen a dramatic increase in the diversity of
research in the area of metal-containing macromolecules. In addition to
original research articles, there are a number of reviews and books that
discuss the developments in this exciting field 1-10.
Phthalocyanines (Fig.1.1) are planar, macrocyclic aromatic compounds
isoelectronic with porphyrine molecule consisting of four isoindole units
linked together by nitrogen atoms11-15. They are tetrabenzo[5,10,15,20]tetraazaporphyrins 16 . They are pigment dyes that contain -electron system
in the molecular structure which provide them unique spectroscopic and
photoelectric properties, and they have received extensive attention due to
their peculiar and unconventional chemical and physical properties. They
form an important class of macrocyclic compounds which do not occur in
nature 17,18. Phthalocyanines are mans analogues of natures pigments of life,
the porphyrins, such as chlorophyll and hemoglobin 19,20. Moreover, they
were one of the first macrocyclic substances that were synthesized in
laboratories. There are 16 possible sites for macrocycle substitution
associated with four benzo-subunits. Substitution in eight peripheral
positions (2,3,9,10,16,17,23,24-substituted phthalocyanines), with long
chains yields more readily soluble phthalocyanines than unsubstituted
phthalocyanines (which almost do not dissolve in common organic solvents
like dichloromethane or acetone) 21-28.
They are important nitrogen containing planar 18 -electron heterocyclic
conjugated compounds 29. Among tetrapyrrole compounds, phthalocyanines
which are full-aromatic molecules, due to these -electron their structure are
not only capable of undergoing classical displacement reactions, but they

can also be substituted with a great deal of functional groups 17,30,31 .
Fig.1.1: Phthalocyanine structure

1.1.1. Discovery and history of phthalocyanine
Serendipity is defined as the accidental discovery of something fortunate
while looking for something entirely different. This was the case of with the
discovery of phthalocyanines (Pcs) at the Grangemouth plant of scottish
Dyes Ltd by Braun and Tcherniac as a by-product during the industrial
preparation of ortho-cyanobenzamide (2) from phthalamide (1) in acetone
(Scheme 1.1), where the glass-lined reaction vessel cracked, exposing the
outer steel casing to the reaction resulting in the formation of blue-green
2
material 32,33. However, no attention was given to the discovery at that time.
Later, due to academic interest the study of this compound was taken up by
Professor J. T. Thorpe who gave it to Reginal Patrick Linstead (1902-1966)
for investigation. Using a combination of elemental analysis, molecular
mass determination and oxidative degradation, Linstead was able to come up
with the correct structure for this material 34.
Scheme 1.1: First preparationof a metal-free phthalocyanine

Phthalocyanine compound was investigated meticulously by Linstead 35. He
was the first to use the term phthalocyanine 35, deriving the name from the
Greek words naphtha (rock oil) and cyanine (blue). In subsequent years,
using a variety of analytical techniques, the structure of phthalocyanine was
clarified 36. Robertson later confirmed Linsteads structure by using X-ray
crystallography, showing that the Pc molecule is planar rather than threedimensional 37.
1.1.2. Structure of phthalocyanine

Phthalocyanines (3) belong to the tetrapyrrole macrocycle class, with the
structure containing an alternating nitrogen atom-carbon atom ring. This
class includes porphyrins (4) and porphyrazines (5) 38.
Fig.1.2: Molecular structures of tetrapyrole macrocycles

Phthalocyanines (3) consist of four isoindoline units linked together at the
1,3- positions by aza bridges. Phthalocyanines possess large nonlinearity,
along with synthetic flexibility as well as thermal stability. The molecule has
a conjugated, 18 electron aromatic planar structure. This system, which
is localized over alternate carbon and nitrogen atoms, provide the unique
chemical and physical properties attributed to Phthalocyanines . In addition,
there are 16 possible sites of substitution on the fused benzene rings, which
allow incorporation of different substituents on the peripheral {(2,3), (9,10),
(16,17) or (23,24)} or non-peripheral {(1, 4), (8,11), (15,18) or (22,25)}
positions of the ring (Fig.1.2), (Fig.1.3).
Fig.1.3: Numbering scheme for phthalocyanine

Phthalocyanines can host different elements in the central cavity 39, forming
metallophthalocyanines (MPcs). The presence of a metal atom in the
Phthalocyanine central core allows for axial ligation. Axial substitution in
Phthalocyanine complexes generally increases solubility, reduces molecular
aggregation and evokes relevant changes to the electronic structure of the
molecule by altering the -electron distribution attributed to the dipole
moment of the central metalaxial ligand bond 40.
The coordination of the Phthalocyanine ligand with metal and metalloid

elements results in an alteration of molecular conformation 41.
Phthalocyanines metallated with heavy metals show a domed
conformation41,42 . The essentially planar conformation of Phthalocyanines
can also be distorted by substituents alone, through conformational stress 43.
In recent years there has been enormous interest in the fundamental
properties of phthalocyanine chemistry. Traditional uses for phthalocyanines
are as colorants and as blue and green pigments 38.
1.1.3. Preparation of phthalocyanines
In general, phthalocyanines are prepared by
cyclotetramerisation of the starting material. A number of
ortho-disubstituted benzene derivatives can act as Pc
precursors. Most precursors are derived from phthalonitrile
(1,2-dicyanobenzene), phthalic acid, phthalic anhydride,
phthalimide, diiminoisoindoline, o-cyanobenzamide, odibromobenzene and other derivatives (Scheme 1.2)
44
Scheme 1.2: Synthetic routes of MPcs from starting

materials
1.1.4. Purification of Metal Phthalocyanines
A formidable hurdle in phthalocyanine chemistry is the isolation of
phthalocyanine in its pure form. Every method of preparation of
phthalocyanines results in the contamination of the product with unreacted
materials such as phthalic anhydride, urea, phthalimide or phthalonitrile. The
phthalocyanine formed itself is a mixture of oligomers. Classical purification
techniques such as acid and alkali washing, solvent washing, solvent
extraction, regeneration by concentrated H2SO4, vacuum sublimation and
chromatography are used to purify the crude phthalocyanines.
8
The first step in the purification of phthalocyanine involves washing with

10% caustic soda, 2M HCI, methanol and benzene successively. The solid
mass so obtained is slurred in concentrated sulphuric acid and dropped on
ice. The precipitate which is essentially a mixture of various polymorphs of
metal phthalocyanines is washed with water and dried. Though this method
is sufficient for the removal of unreacted materials, the different polymorphs
and oligomers cannot be separated.
Linstead et al 45 have reported that phthalocyanines sublime under vacuum
slowly at 550 0C and rapidly at 580 0C. This method is found suitable to
prepare very pure crystals and thin films of metalphthalocyanines. The
vapour is deep blue and the crystals formed have the purple luster. These
films of metalphthalocyanines of thickness 1000-4000 A can be
conveniently prepared by sublimation technique.
1.1.5. Aggregation of phthalocyanines
Phthalocyanines tend to aggregate in solution due to the strong electronic
interactions present between planar macrocycles 46,47. Aggregation is usually
depicted as a coplanar association of rings progressing from monomer to
dimer and higher order complexes and is driven by enhanced van der Waals
attractive forces between phthalocyanine rings 48,49. In the aggregated state,
the electronic structure of the phthalocyanine rings is perturbed, resulting in
an alteration of the ground and excited state properties 50. Aggregation in
phthalocyanines is characterized by a broadening of the Q-band with a
corresponding blue- (H-aggregate 51) or red-shift (J-aggregate 52) in their
wavelength values or by splitting of the Q-band. These spectral effects will
depend on the proximity of the rings, the bulkiness of the substituents, the
tilt angle of the rings, the overlap position, in addition to the other factors
which determine the -electron cloud overlap.
9
The H-aggregate 51 is a cofacial arrangement, which readily allows

Phthalocyanine macrocycles to stack on to top of each other. On the other
hand, the J-aggregates are an edge-to-edge arrangement 52.
The overlap of -electron clouds of dimers results in a split in the LUMO
orbital (Fig. 1.4). According to the excitation coupling theory, transitions to
higher energy states (1Eu) are allowed (H-aggregates), whereas transitions to
lower energy states (1Eg) are forbidden (J-aggregates) 53. The transitions to
lower energy LUMO orbitals can still occur to a small extent, even though
they are forbidden, resulting in a broad absorption band. It is thus rare to
observe J-aggregates in phthalocyanines.
Fig. 1.4: Electronic transitions in phthalocyanines aggregates
10
Aggregation behaviour of Phthalocyanines is generally investigated by

concentration-dependence, as well as, solvent studies. Dilution of the
Phthalocyanine solution generally leads to the formation of the monomeric
species 54. Addition of a surfactant, to an aggregated species can result in
dissociation of the aggregates 50.
Many workers 55-58 have studied the dimerization and aggregation of
substituted phthalocyanines. The orientation and packing of the
phthalocyanine units can be controlled, using Langmuir-Blodgett technique
of monomolecular layer formation and transfer. As monomolecular layer
films, phthalocyanine compounds display properties like electrical
conductivity, electrical switching between conducting states, photovoltaic
effects, oxidative catalytic activity etc. The full utilization of LangmuirBlodgett technique requires soluble phthalocyanine compounds, the ability
to modify them chemically and knowledge of their solution and solid-state
molecular aggregation 59. The data presented below relates to soluble metal
tetrasulphophthalocyanine. The molar absorptivities of the monomer and
dimer in 50% ethanol at 697 nm are 9.98x l04 M-1 cm-1 and 3.22 x104 M-1 cm1
respectively. The concentration equilibrium constant for dimer formation,
Q D is given by:
11
Where (M) and (D) are the molar monomer and dimer concentrations,
respectively, M and D are the monomer and dimer molar extinction
coefficients, CT is the total concentration of the phthalocyanine tetrasulfonate
anion, 0 is equal to the absorbance A for the equilibrium mixture divided
by CT. The dimer formation constant of phthalocyanine tetrasulfonate anion
in its 1.0 M solution in 20 % aqueous ethanol is 8.1 X l05 in 1.0 M HCl.
Addition of HCI, HClO4, NaCl and LiCl markedly affect the spectrum of
aqueous solutions of the dimer. The effect was reported in terms of tetramer
formation and tetramer formation constants 60. The aggregates of vanadyal
complex of tetrasulfophthalocyanine exist in aqueous solution at relatively
high concentrations used (0.01- 0.04M) and dimeric complex is formed as
dimethylformamide is added 58. It is also found that small amounts of
NaCIO4 stabilize the dimer of the other tetrasulphophthalocyanine and that
large amounts of NaC1O4 cause further aggregation 61.
1.1.6. Technological Applications of Phthalocyanines
Phthalocyanines are aromatic compounds owing to their planar conjugated
display of 18 -electrons. They are used in a number of applications because
of their increased stability, architectural flexibility, diverse coordination
properties and improved spectroscopic characteristics. They are applied in
fields such as:
1.1.6.1. Pigments and Dyes
Phthalocyanines are highly delocalized 18- electron aromatic molecules
showing strong absorption in the visible region, for this reason, they are
extensively used as dyestuffs for textiles and printing inks 17,62. Their
characteristic blue-green color and robustness account for their traditional
use as industrial dyes pigments 63,64. phthalocyanines are second only to the
12
ubiquitous azo colorants in terms of commercial importance. The major

commercial impact of phthalocyanines is based on three factors; the first is
their beautiful bright blue to green colors and high tinting strength; the
second is their remarkable thermal and chemical stability. The third factor is
their excellent fastness to light. This combination of properties is extremely
difficult, if not impossible, to achieve in other colorants. By comparison, the
natural dyes such as chlorophyll and haemin are highly sensitive and easily
destroyed by light and mild chemical reagents 65.
They are widely used in paint and plastic industries. The noncolorant
applications include catalysts, lubricating greases, analytical reagents,
clinical diagnostic agents and electrical devices.
Although the shade range of the phthalocyanines is rather limited and covers
only the blue-green regions of the spectrum, their excellent fastness to light,
and high absorptivity render them apt for many applications. The insolubility
of phthalocyanines necessitates preparation of soluble derivatives for
application as dyes for textile fibres. Phthalocyanine pigments in the form of
aqueous dispersions are used in pad-dyeing with resin emulsions. Because of
their excellent stability to acids, alkalis and solvents phthalocyanines are
particularly useful in spin dying. They have also been used in coloring
polyvinylchloride fibres, viscose, cuprommonium cellulose, nylon, etc,
Phthalocyanines have found wide use as paint pigments. Metal surfaces can
be coated by forming the metal phthalocyanine directly on them 66. Large
metal surfaces can be coated with metal phthalocyanine by dipping in a
solution of phthalonitrile in acetone, drying, and subjecting the metal to
temperatures of around 350 0C in a sealed oven. The coating is very adherent
and the shade of colour depends on the metal used.
13
Phthalocyanines have been used to color rubber, poly styrene, poly urethane
foams, cellulose acetate sheeting, polysters, polyamides, vinylchloride
polymers and other plastic and polymeric materials 67-70. Copper
phthalocyanine-sodium sulfonate has been used in photographic processes to
produce colored prints. Copper phthalocyanine is also used as a certified
food color 71.
1.1.6.2. Analytical Reagent
Copper phthalocyanine in concentrated sulphuric acid has been used as a
reagent for the detection of oxidizing agents such as NO2- , NO3- , CIO3- ,
BrO3-, IO3- , Cr2O72- and MnO4-. Copper tetrasulphophthalocyanine is used as
a redox indicator in the cerimetric determination of iron (II) and
ferrocyanide 72. It was found that copper 4,4',4",4'" tetrasulphophthalocyanine (CuTSP) is a suitable indicator for the titration of Fe(II) in 0.5 - 2 .5
M HCI or H2SO4 or Fe(CN)6 4- in 0.5 N H2SO4 with 0.0I N to 0.00l N Ce 4+ .
CuTSP is stable towards HCl, H2SO4 and H3PO4. A 0.1 % solution of CuTSP
is used as the indicator solution.
1.1.6.3. Catalyst
The first mention of phthalocyanines as catalyst is on the activation of
molecular hydrogen 73 and found that crystals of phthalocyanine and copper
phthalocyanine catalyze atomic interchange between molecular hydrogen
and water vapour, and oxygen 74. Phthalocyanines catalyze the oxidation of
many organic compounds 75-77. Also they catalyze the oxidation of -pinene
to verbenone, and the autooxidation of saturated ketones such as 2-octanone,
4-heptanone and cyclo hexanone at 120-130 0C to -diketones and aldehyde.
The aerobic oxidation of unsaturated fatty acids catalyzed by
phthalocyanines has been reported 78. Cobalt and other phthalocyanines
derivatives have been used as rubber emulsification catalysts. When cobalt
14
tetrasulphophthalocyanine is attached to poly (vinylamine) it can catalyses

the autooxidation of thiols 79.
1.1.6.4. Electrocatalysts
-Keto acids, eg. pyruvic, phenylpyruvic, -ketobutyric, -ketoglutaric and
-keto isocaproic undergo electrocatalysed reduction at carbon past
electrode modified with cobalt phthalocyanine 80. CoPc modified electrodes
can catalyse numerous electron transfer processes in addition to those of
hydrazine and thiol compounds 81 Metal phthalocyanines have received
much attention in the electocatalytic reduction of dioxygen82-84.The
phthalocyanines assume importance in electrocatalysis for two reasons:
a) Metal phthalocyanines are structural and electronic analogues of
porphyrins whose electrochemistry is important in understanding electron
transfer processes in biological systems.
b) Electrocatalytic reduction of dioxygen is important in fuel cells 85.
Because of the lower solubility of phthalocyanines, water soluble
phthalocyanines such as tetrasulphophthalocyanine 86 , and tetracarboxy
phthalocyanine 87, have been used as facile catalysts in aqueous medium.
The electrocatalytic activity of dioxygen reduction was improved at a glassy
carbon electrode when modified with polypyrrole /tetrasulfonatophthalocyaniato cobalt electrode 88. The glassy carbon /polypyrrole/cobalt
tetrasulfophthalocyanine (GC/PPY /CoTSP) electrode was formed by
electropolymerization of pyrrole on a glassy carbon electrode in methanol
solution containing CoTSP. Oxygen reduction reaction at the
GC/PPY/CoTSP electrode in O.5 M H2SO4 showed about O.5 V more
anodic onset potential than the value obtained with a GC electrode in the
same medium.
15
The reduction of dioxygen at iron tetrasulfonatophthalocyanine (FeTSP)

incorporated into polypyrrole was also studied 89. It was found that thicker
films are stable and mediate four-electron reduction of dioxygen. It was
indicated that dimeric FeTSP species are responsible for the marked shift in
the reduction onset potential.
Polymeric iron phthalocyanine precipitated on activated carbon, when
heated to 200-500 0C showed a higher rate of deactivation for the
electrochemical reduction of dioxygen 90.
The iron phthalocyanine functions as a catalyst layer and oxygen sensor in
fuel cells and air battery 91. A porous electrocatalyst material was prepared
by soaking activated carbon in iron phthalocyanine pyridine solution and in
perfluorodecalin CCl4 solution and then mixing with PTFE. The material
in the form of sheet was bonded on a nickel mesh. The electrode was used in
a zinc-air battery having a discharge current density of 63 MAm2.
1.1.6.5. Active Layers on Chemically Modified Electrodes
Electrodes derived from different types of phthalocyanines have been
fabricated 84,92-94, powdered carbon or metal is coated with the
phthalocyanines by chemical vapour deposition, solvent evaporation or
electrophoretic deposition. The powder of the same material has also been
pressed with crystalline phthalocyanines into composite pellets. Various
metal and semiconductor substrates demonstrated greatly enhanced activity
for the electrolysis of the benzoquinone/hydroquinone redox couple when
coated with multimolecular layers of chlorogallium phthalocyanine 95.
Exchange current density on GaPc-Cl Au electrode irradiated with ~
100mW/cm2 polychromatic light were ~ 103 times greater than on plain gold
electrode. The role of GaPc-Cl in activating the substrate surface is also
reported. The use of chemically modified carbon paste electrodes, which
16
are modified by the incorporation of cobalt phthalocyanine is able to oxidize

or reduce solute species which are themselves electrolysed only irreversibly
at conventional electrode surfaces." These electrodes decrease the over
potential for the oxidation of thiols 96, hydrazine 97, -keto acids and oxalic
acid. A glassy carbon electrode modified with CoPc can be efficiently used
as a liquid chromatographic detector for the clinical assay of oxalic acid and
a-ketoacids in blood and urine. Faulkner et al 98,99 have studied in detail the
faradaic processes taking place on Pc modified electrode surfaces. Nearly
reversible kinetics and a high degree of selectivity for the electrode process
are observed on these films.
Preduction of dioxygen takes place on certain phthalocyanines, when they
adhere vacuum deposited to a thickness of 100-1000 A0 on polished
graphite. Photooxidation of oxalate takes place on 1 mm thick films of CuPc
deposited on Pt 100.
Furthermore, phthalocyanines are useful for anode buffer layers 101,102 , and
can be used for emitting layers 103.
1.1.6.6. Photovoltaic and Photogalvanic Devices
Phthalocyanines show photoconductivity. The photoconductive and
photovoltaic properties of Phthalocyanines have been studied for use in
electrophotographic systems, diodes, laser printers, photovoltaic cells,
photoelectrochemical devices and vidicon tubes 104-108.
Cobalt (II) tetrasulfophthalocyanine (CoTSP) can be covalently bound to the
surface of titanium dioxide particles. Upon irradiation with light having
energy exceeding the band gap energy of TiO2, Co(II) TSP is reduced to
Co(I) TSP. This photochemical reduction is reversible in presence of
dioxygen. The photochemical stability and the high quantum yields for O2
reduction makes this newly developed material applicable as a potent and
17
stable oxidation catalyst. The interest shown in these systems is due to the
simultaneous formation of dihydrogen and dioxygen from water. An overall
transfer of conduction band electrons e -cB and valence band holes h +vB is
required to achieve this direct storage of solar energy in the form of
chemical energy. The reactions taking place are:
2H2O + 2e cB H2 (g) + 2OH aq (cathodic)
2H2O + 4H + vB O2 (g) + 4H + aq
(anodic)
Cobalt tetrasulfophthalocyanine covalently bound on the surface of titanium

dioxide particles act as efficient electron relays to compete with the e -/h +
recombination and thus achieve reasonable but still rather small, quantum
yields.
Efficient organic solar cells 109 , and field effect transistors also have been
fabricated using various phthalocyanines.
In photocells, with phthalocyanine as the active material under an externally
impressed negative bias, the efficiency in energy conversion can reach about
25% 110,111.
1.1.6.7. Electrochromic Displays
Electrochromic (Electrochemichromic EC) effect is the production, by
faradaic reaction, of a color change in materials localized at an electrode
surface. A thin film of metal diphthalocyanine deposited on optically
transparent electrode shows change in absorption spectrum of polarisation in
contact with an aqueous electrolyte 112,113.
18
Electrochromism of phthalocyanines are very interesting for developing new

type displays and have been investigated for many years 114,115.
1.1.6.8. Batteries
Phthalocyanines and phthalocyanine derivatives have been used as cathode
materials in batteries especially in fuel cells and air cathode batteries. In
batteries the porous electroconductive material is loaded with metal
phthalocyanine and a perfluoro compound. This composite material is
used as the catalyst layer 116,117.
1.1.6.9. Gas Sensors
Devices based on metal phthalocyanine show useful response towards NO2.
A thin film MPc sensor has successfuly been used to monitor NOx produced
by short firing in coal mines 118. Phthalocyanine based devices offer much
promise as resistance modulating sensors for toxic gases, sensors against
toxic gases can be developed using the conductivity changes of
phthalocyanines 119,103. They are thus complementary to metal oxide devices
which are most useful in the detection of flammable gases 120.
I.1.6.10. Electrophotography
Electrically conductive substances are coated with photoconductive layers
made up of phthalocyanines dispersed in a binder resin; the plates show high
sensitivity, improved durability and excellent imaging characteristics121.
Attention has been focused on potential application - (scheme. 1.3) - of
phthalocyanine in industry due to their physical and chemical stability.
Phthalocyanine is one of the most thermally stable substances 122,123. Very
high thermal stability of the phthalocyanine molecule is due to its extremely
high aromatic character which exceeds that of a benzene ring by a factor of
15 as reported by Lansdale 124. In addition to the excellent thermal stability
of phthalocyanine, properties like chemical inertness, very high tinting
19
nature, semiconductivity, photoconductivity and catalytic activities have

prompted to prepare various types of thermally stable metal phthalocyanine
polymers 125-143.
Metal phthalocyanines are class of compounds attracted world-wide interest
because of their interesting properties like chemical inertness, excellent
thermal stability, very high coloring properties, catalytic activity,
semiconductivity, photoconductivity and the like 11,18,144-146. Electrical
conductivity is one of the important properties of the phthalocyanine
compounds which attracted great deal of interest 147,148. Extensive research
work has been carried out to improve the electrical conductivity of
phthalocyanines via doping mechanism and polymerization methods 144-146,149154
. The effect of substituents and the peripheral phenyl groups of the
phthalocyanine structure seems to yield much information about the nature

of electrical conductivity of complexes. However, work done in this
direction is meagre. In 1991, Singerski et al 155, studied the electrical
conductivity of nickel (II) tetra-amino phthalocyanine. Among the effect of
various substituent groups on the electrical conducting property of
phthalocyanine, amine group substituent on the peripheral benzene ring of
the phthalocyanine molecule has been found to increase electrical
conductivity to a greatest extent 156-161.
The use of phthalocyanine has recently extended to many high technological
processes. They can be used in many applications with appropriate
substitution in the peripheral position of the macrocycle, such as in optical
recording materials, optical limiters, field-effect transistors, LangmuirBlodgett films, 162 thin films (or solar cells), 163 gas sensors, 164 and liquid
crystals. 165 Furthermore, they are used as catalysts for photo or oxidative
degradation of pollutants, and as photosensitizers 166. They have attracted
20
great attention because of their versatile applications 16,17,167. One of their

most promising aspects is functioning as photosensitizers for photodynamic
therapy of cancer or photodegradation of pollutants 168,169. The most
fundamental property of a photosensitizer is able to generate reactive oxygen
species (ROS), in particular singlet oxygen, under light irradiation 168. The
photosensitized ROS production of phthalocyanines is strongly affected by
the nature of their central metal ions 170. The phthalocyanines coordinated
with closed shell, diamagnetic ions possess high ROS yield 171. Otherwise,
the photosensitizing efficiency of the phthalocyanine is largely influenced by
its molecular aggregation 169,172. Molecular aggregation of phthalocyanines,
which is an intrinsic property of these large -conjugated systems, provides
an efficient non-radiative energy relaxation pathway, thereby shortening the
excited state lifetimes and greatly reducing the photosensitizing efficiency
170b,173
The discovery of semiconducting properties of metal

phthalocyanines by Eley and Vartanyan
172
, created interest
in the electrical properties of phthalocyanines which has

grown steadily with their increasing potential advantages
day by day. Extensive research work is going on to improve
the electrical conductivity of phthalocyanines by replacing
two central hydrogen atoms of metal free phthalocyanine by
different elements, doping, polymerization and by attaching
substituents on the peripheral phenyl groups of the
phthalocyanine structure
18,172-176
Electrical conductivity of metal phthalocyanines is very

sensitive to structural alterations and presence of impurities
177
.
21
Phthalocyanines are an important class of organic materials

with a very stable electronic configuration which makes
them an important class of functional materials
17
Phthalocyanine chemistry is undergoing a renaissance

because phthalocyanines and many of their derivatives
exhibit singular and unconventional physical properties
which are interesting for applications in materials science
They can be used in photonic devices
179,180
178
and because of
the flexibility in tailoring the electrical and optical properties,

phthalocyanines can be used in many devices like: fuel cells,
organic metals, electronic media, photoelectrical detectors
xerographic media, field effect transistors
diodes
182-184
displays
181
, light-emitting
, optical recording, optical memories, information
185
, hole-burning memories, light-limiters, lasers,
non-linear optical elements, etc.
186
. The photoactive semi-
conducting properties of phthalocyanine monomers and

polymers makes possible the production of low cost, flexible
187,188
. In organic photovoltaic devices, dissociation of photo-
generated excitations occurs leading to photocurrent in the

external circuit
189-191
Since the discovery and invention of intense light sources

based on laser mechanisms in the 1960s, the need for the
development of protective devices against laser radiation
has stimulated essential research, due to the widespread use
22
of laser weapons. Thus eye and sensor protection systems

are required due to intentional laser misuse, which, for
example, has resulted in temporary blindness of pilots upon
approach to landing (Fig 1.5). There have also been several
laser induced eye injuries that have occurred in the U.S.
military between 1984 and 2000, caused by accidental
exposure to a Q-switched, Neodynium:YAG (Nd:YAG) laser at
1064 nm wavelength.
Fig.1.5: Laser light on aircraft

Consequently, there is a need to develop highly efficient
protective devices, in order to provide protection to human
eyes and sensitive sensor systems. For example, the reliance
of the South African army on laser illumination warning and
on training air crew is not adequate because the sensors,
which are currently in use, do not cover the complete range
23
of laser threats and as a result they do not protect the eyes.

Thus the interest in developing efficient and stable optical
limiting material in South Africa.
The structural prerequisite for nonlinear optics (NLO)
material is the presence of a conjugated, delocalized electron orbital network. The conjugated structure affords
high polarizability properties and thus fast charge
redistribution on interaction with intense magnetic radiation,
such as laser radiation. Organic and organometallic
materials have emerged as promising candidates for limiting
laser radiation intensity. Among NLO materials, metal
phthalocyanines are of great interest because they have
several advantages over the inorganic material currently in
use for optical limiting (OL). The Laser light advantages
include: i) fast response times (subpicosecond), the faster
the response is, the better the optical limiter small dielectric
constants ease of fabrication or processing and low cost of
production. The discovery of phtalocyanines as active NLO
materials in optical limiting applications has been widely
recognized. Up until recently, the feasibility of
Phthalocyanines as NLO materials has been devoted to the
measurements of NLO properties, together with a basic
understanding of the origin of nonlinearities
192
For clinical photodynamic therapy (PDT), the

photosensitizers such as hematoporphyrin derivatives (HpD)
and Photofrin have been used exclusively to date
24
193
However, as these compounds absorb light of relatively short

wavelength, and the penetration depth of short-wavelength
light in tissue is relatively shallow, the benefits of current
PDT are limited to shallow tissues only
194,195
. Therefore
compounds with absorption bands of longer wavelength are

more adequate for PDT. Since phthalocyanines exhibit
advantageous photophysical properties for PDT such as
photostability, long lifetimes of the photo excited triplet
state, and high molar absorption in the red region of the
visible spectrum, high efficiency to generate reactive oxygen
species (such as singlet oxygen), and low dark toxicity, they
may be quite advantageous as photosensitizers
treatment of cancer
196,197
, in the
198-200
, and intimal hyperplasia201.
Phthalocyanines have also been used in photo-inactivation of

viruses
202-204
. PDT dyes are recognized as efficient sensitizers
of singlet oxygen and the involvement of singlet oxygen in

the PDT process is now widely accepted.
Finally, certain derivatives of phthalocyanines have shown
promise as photodynamic reagent for cancer therapy and
other medical applications
205
25
Scheme 1.3: Potential applications of phthalocyanines

in industry
1.1.7. Geometry of phthalocyanine

The geometry (Fig.1.6) of a metal-free phthalocyanine is square planar, i.e.
D2h symmetry. If the planarity is maintained when a metal, which fits inside
the phthalocyanine cavity, incorporated into the phthalocyanine ring, the
symmetry increases from D2h to D4h. Larger metal ions tend to distort the
26
geometry of the macrocycle, forming C4v symmetry. This symmetry is a

result of the rotation of the rigid isoindole units that reduce the internal
stress induced by the large metal size 38.
Tetrasubstituted phthalocyanines can be formed from monosubstituted
precursors. These substituted phthalocyanines lead to constitutional isomers
which form as a result of the symmetry involved in the condensation
reaction for phthalocyanine preparation 206. (Figure 1.7)
Fig.1.6: Geometry of phthalocyanines
27
Fig.1.7: Constitutional isomers of non-peripherally substituted MPcs.
28
1.1.8. UV-Visible Spectroscopy

Transition metal compounds display a wide variety of colors
and many of these compounds are used as artists pigments.
The color of these compounds is due to electronic transitions
induced by the incident light, causing absorption at certain
wavelengths, depending on the structure and bonding in the
molecule. UVVisible spectroscopy is used to quantities the
absorption properties of molecules.
The electronic transitions of transition metal compounds can
be categorized into three types: charge transfer, dd spin
allowed and dd spinforbidden. Charge transfer bands occur
when the excited electron moves from a metal centered
orbital to a ligandcentered orbital (metaltoligand charge
transfer MLCT) or when the excited electron moves from a
ligandcentered orbital to a metal centered orbital (ligand
tometal charge transfer LMCT). MLCT bands are more
common than LMCT. Spinallowed and spinforbidden dd
transitions find the excited electron moving from one d
orbital to another d orbital. In the spinallowed transition the
spin quantum number (or more accurately, the spin angular
momentum) in the ground and excited states are the same
while in the spin forbidden transition the spin state changes
during the excitation.
UVVis spectra can be used to investigate both the
geometric structure and the electronic structure (i.e., the
29
nature of the bonding) in transition metal complexes. Most

spectra are measured in solution and this leads to broad
absorption bands that give rise to few structural details.
Because of this, only the most general structural conclusions
can usually be deduced. One exception to this statement is
the optical titration experiment where a series of spectra are
recorded as a function of added reactant (usually the ligand
is added to the metal). The Observation of isosbestic Points
(wavelengths
where all of the spectra intersect, independent of the
concentration of the added reactant) means that there is a
well defined limit to the number of absorbing species in
solution and with this information the structure of the
solution species can often be deduced
207,208
1.1.8.1. Electronic structure and spectroscopy of

phthalocyanines
There are various methods used for the characterization of phthalocyanines.
Such methods include infra-red spectroscopy (IR), elemental analysis, mass
spectroscopy and others. Of all these methods Ultraviolet-visible
spectroscopy (UV-Vis) is the most popular form of phthalocyanine
characterization. The method give an indication of what is known as the Qband that is of particular importance. The Q-band is a characteristic
absorption peak for phthalocyanines and its position is largely influenced by
the central metal atom and the substituents on the phthalocyanine ring 209.
The spectral properties of phthalocyanines arise due to the 18- conjugated
ring system as shown in Figure 1.8.
30
Fig.1.8: Molecular structure of a MPc showing the

path of the 18- conjugated system used
31
1.1.9. Infrared Spectroscopy

Infrared spectroscopy is one of the most important physical
characterization techniques used by the chemist. It can be
used for identification of compounds, elucidation of bonding
characteristics, and for quantitation of species. The most
frequent application of IR spectroscopy is the identification of
a compound, a particular ion or chemical functionality.
Infrared absorptions arise because vibrations in the molecule
that cause a change in the dipole moment of the molecule
absorb the incident radiation. In a (heteronuclear) diatomic
molecule a single vibrational peak may be found in the IR
spectrum since only one vibration exists. This vibration can
be modeled by considering the bond as a spring (a harmonic
oscillator) and then use of Hook's law gives the energy of the
vibration in terms of the spring constant. The molecular
parameter associated with the spring constant is called the
force constant and is a measure of the bonding in the
molecule. Hook's law also involves the mass of the atoms
connected to the end of the spring so that vibrational
frequencies are identified with two characteristics: atomic
masses and bond strength. In more complex molecules these
force constants are similar for a series of the same atoms
bonded in the same fashion (e.g., the force constants for a C32
C single bond are similar for most molecules) so that

vibrational peaks for a given type of bonding always show up
in the same region of the spectrum; for example, CO absorbs
in the 1700 to 2150 cm-1 region for virtually all complexes.
These are called group frequencies and are useful for
structure determination of new compounds.
Two types of group frequencies are especially important to
the study of metal complexes: metal-ligand stretches and
carbonyl stretches. Both occur in spectral regions with few
other absorptions (metal-ligand stretches are found in the
200-550 cm-1 region and CO as noted above) so that they are
observed with few interferences.
Since bond strength and atomic masses determine
vibrational energies, the position of the metal-ligand
stretching depends on both the metal atom and ligand atom
involved. As the masses of the bonded atoms increase the
vibrational frequency decreases; as the bond strength
increases so does the IR absorption frequency
210,211
1.1.10. Thermogravimetric Analysis (TGA)

Thermogravimetric Analysis (TGA) is a technique in which a
physical property of a substance and/or its reaction products
is measured as a function of temperature whilst the
substance is subjected to a controlled temperature Program
212
. The resulting mass-temperature profiles are known as
thermograms. The balance pan and sample are enclosed

within a small closed oven to: (i) ensure that accurate, stable
33
and uniform temperatures may be achieved and (ii) prevent

thermal conduction air currents that will affect the balance.
Weight variation in the order of micrograms can be easily
followed. The balance should be calibrated each time it is
used with a known mass; this deflection is normally recorded
in the thermogram curve
213
. Thermograms may be (i) a
thermogravimetric (TGA) curve, in which the weight change

is recorded as a function of temperature or time, or (ii) as a
derivative thermogravimetric (DTA) curve where the first
derivative of the TG curve is plotted with respect to either
temperature or time
214
1.1.11. Mass spectrometry

In 1911, J.J Thomson used a mass spectrum to demonstrate
the existence of neon -22 in a sample of neon-20, thereby
establishing that elements could have isotopes. The earlier
mass spectrometer, as we know it today, was built in 1918.
However the method of mass spectrometry did not come
into common use until quite recently, when reasonably
inexpensive and reliable instruments became available
215
The concept of mass spectrometry is relatively simple. A

compound is ionized, the ions are separated on the basis of
their mass to charge ratio, and the number of ions
representing each mass to charge unit , is record as
spectrum
216
The mass spectrometer performs three essential functions.

First it subjects molecules to bombardment by a stream of
34
high energy electrons, converting some of the molecules to

ions , which are accelerated in an electric field, second the
accelerated ions are separated according to their mass to
charge ratios in a magnetic or electric field. Finally, the ions
that have a particular mass to charge ratio detected by a
device which can count the number of ions striking it. The
detector's output is amplified and fed to a recorder. The
trace from the recorder is a mass spectrum a graph of the
number of particles detected as a function of mass to charge
ratio
215
1.1.12. Magnetic Properties

Magnetic susceptibility measurements of metal
phthalocyanines give information relating to their structure
and the nature of bonding of the central metal atom with the
surrounding isoindole nitrogen atom
217
1.1.13. Solubility of phthalocyanines

In recent years there has been enormous interest in the
fundamental properties of phthalocyanine chemistry
38
. The
solubility of phthalocyanines is the most important feature of

the complexes for theirs possible applications and for
investigation of their chemical and physical characteristics
218
The poor solubility of phthalocyanines in most organic

solvents is due to strong interactions which cause
aggregation of the Phthalocyanines 206. The presence of a
35
metal atom in the phthalocyanine central core allows for

axial ligation. Axial substitution in phthalocyanine complexes
generally increases solubility, reduces molecular aggregation
and evokes relevant changes to the electronic structure of
the molecule by altering the -electron distribution
attributed to the dipole moment of the central metalaxial
ligand bond
40
Introduction of substituents into the phthalocyanine

framework reduce the intermolecular attractions due to an
increase in the distance between stacked molecules 219. The
steric hindrance caused by substitution encourages
phthalocyanine dissolution in a solvent and this greatly
improves solubility. The importance of the preparation of
substituted phthalocyanines is the development of new
derivatives that have improved chemical properties
206
Two types of substituted macrocycles can be distinguished

according to their substituent positions. These are:
substitution at the more sterically crowded (nonperipheral) position and substitution at the (peripheral)
position (Fig. 1.9 insert). The former causes reduced
aggregation tendencies to greater extent than the later
220
Phthalocyanines may be tetra- or octa-substituted, where

tetra-substituted phthalocyanines are usually more soluble
than the corresponding octa-substituted phthalocyanines
due to the formation of constitutional isomers (Fig.1.7), and
36
the high dipole moment that results from the unsymmetrical

arrangement of the substituents at the periphery
221
Fig.1.9: Substituted and positions in MPcs.

The insert shows the and positions for MPc
1.1.14. Metal phthalocyanines (MPcs)
In spite of the fact that there are many research in the past
decades, essential details of the electronic structure and the
excitations of the MPcs remained unknown, which is
contrasted by the profound importance of the electronic
properties for the physical behavior of these materials.
Transition metal phthalocyanines as carbon-based molecules
are build by a well defined and very stable -conjugated
macrocycle ring (abbreviated Pc for the phthalocyanato ion
37
C32H16N8 2- ). The structure of a TMPc is shown in Fig. 1.10.

They are characterized by the presence of a transition metal
(M) ion in the formal oxidation state 2+ in their central
cavity, which is surrounded by four pyrrole nitrogen (N1),
four bridging aza nitrogen (N2), eight pyrrole carbon (C1) as
well as 24 benzene ring carbon (C2, C3, and C4) atoms.
Thereby, the phthalocynine ring acts as ligand to the central
transition metal ion, and the Pc 2- ligand forms a neutral
complex with the divalent transition metal ions, whereas the
bonding between the ligand and the central transition metal
ion is also significantly covalent
222
. TMPcs have a planar
structure with D4h point symmetry. Under the consideration

that the molecules are placed in the xy-plane, the five metal
3d orbitals transform as a1g (dz2) , b1g (dx2-y2) , eg (dxy), i.e., dxz
and dyz), and b2g (dxy). Thereby, the energetic order of the
orbitals depends on the strength and the type of the
distortion, and on hybridization effects of the metal 3d
orbitals with the ligand orbitals. An a priori determination of
the energetic orbital order is not easily possible, but has to
be verified by experimental investigations. For many
transition metal phthalocyanines there is no complete
microscopic understanding of the electronic and spin ground
state. In particular, there are contradicting predictions and
experiments in regard of the orbital ground state of the
transition metal center
223-230
38
Fig.1.10: Chemical structure of a transition metal

phthalocyanine molecule. With M the central transition metal
ion is denoted, which is surrounded by four pyrrole nitrogen
(N1) and four bridging aza nitrogen (N2) atoms. The 24 carbon
atoms in the outer benzene rings are labeled with C-2, C-3, and
C-4, respectively. With the label C-1 the 8 pyrrole carbon
atoms are denoted.
39
1.1.15. Overview of studied metals

1.1.15.1. Chromium(III)
There are literally thousands of chromium(III) complexes that
with a few exceptions, are all hexacoordinate. The principal
characteristic of these complexes in aqueous solutions is
their relative kinetic inertness.
Ligand displacement reactions of Cr(III) complexes are only
about 10 times faster than that of Co(III) , with half-times in
the range of several hours. It is largely because of this
kinetic inertness that so many complex species can be
isolated as solid and that they persist of relatively long
period of time in solution, even under conditions of marked
thermodynamic instability
231
1.1.15.2. Manganese(II)
The divalent state is the most important and generally the
most stable oxidation state for the element. Manganese(II)
forms many complexes, the majority of these complexes are
high spin
231
1.1.15.3. Iron(II)
Iron(II) forms a number of complexes, most of them
octahedral. In square , four-coordinate complex the extreme
40
tetragonality of the ligand field apparently places one d

orbital (dx2-y2) at high energy, and the six electrons adopt a
high-spin distribution among the remaining four, thus giving
a triplet ground state, independent of temperature
231
1.1.15.4. Cobalt(II)
Cobalt(II) occurs in a great variety of structural
environments; because of these electronic structures, hence
the spectral and magnetic properties of the ion, are
extremely varied.
All square complexes of Co(II) are low spin with magnetic
moments of 2.2 - 2.7 BM at 300o C. Their spectra are
complex, and neither magnetic nor spectral properties of
such compounds have been treated in detail. There are
some data to suggest that the unpaired of electron occupies
the dz2 orbital, as might be expected
231
1.1.15.5. Nickel(II)
Nickel(II) forms a large numbers of complexes encompassing
coordination numbers 4,5and 6, and all the main structural
types (viz, octahedral, trigonal-bipyramidal, square
bipyramidal, tetrahedral and square). Moreover, it is
characteristic of Ni(II) complexes that complicated equilibria,
which are generally temperature dependent and sometimes
concentration dependent, often exist between these
structural types.
For the fast majority of four coordinate nickel(II) complexes,
planar geometry is preferred. This is natural consequence of
41
the d8 configuration, since the planar ligand set causes one

of the d orbitals (dx2-y2) to be uniquely high in energy and the
eight electrons can occupy the other four d orbitals but leave
this strongly antibonding one vacant.
Planar complexes of Ni(II) are thus invariably diamagnetic.
They are frequently red, yellow, or brown owing to the
presence of an absorption band of medium intensity in the
range 450-600 nm, but other colours do occur when
additional absorption bands are present
231
1.1.15.6. Copper(II) state, d9

The dispositive state is the most important one for copper.
Most Cu(I) compounds are fairly readily oxidized to Cu(II)
compounds, but further oxidation to Cu(III) is more difficult.
There is a well-defined aqueous chemistry of Cu 2+, and a
large number of salts of various anions, many of which are
water soluble, exist in addition to a wealth of complexes.
The d9 configuration makes Cu(II) subject to Jahn-Teller
distortion if placed in an environment of cubic (i.e., regular
octahedral or tetrahedral) symmetry, and this has a
profound effect on all its stereochemistry. With only one
possible exception, mentioned below, it is never observed in
these regular environments. When six-coordinate, the
octahedron is severely distorted, as indicated by the data
in table 1.1. The typical distortion is an elongation along one
4-fold axis, so that there is a planar array of four short Cu-L
42
bonds and two trans long ones. In the limit, of course, the
elongation leads to a situation indistinguishable from square
coordination as found in CuO and many discrete complexes
of Cu(II). Thus the case of tetragonally distorted octahedral
coordination and square coordination cannot be sharply
differentiated
231
Table 1.1: Distortion of the octahedron configuration:

Compound
Distances (Ao)
CuCl2
4Cl at 2.30, 2Cl at 2.95
CsCuCl3
4Cl at 2.30, 2Cl at 2.65
CuCl2.2H2O
2O at 2.01, 2Cl at 2.31, 2Cl

at 2.98
CuBr2
4Br at 2.40, 2Br at 3.18
CuF2
4Fat 1.93, 2F at 2.27
[Cu(H2O)2 (NH3)4] in CuSO4.
4N at 2.05, 1O at 2.59, 1O
4NH3- .H2O
at 3.37
K2CuF4
2F at 1.95, 4F at 2.08
1.1.16 Objectives of the search

The aim of this work is chiefly to shed lights on the properties of some
metal-phthalocyanine complexes [ MPc, where M= Cr(III), Mn(II), Fe(II),
Co(II), Ni(II), Cu(II)]. It also aimed to investigate the applications of these
43
metal complexes in biological and antitumor fields. Study the structures of

these complexes and their stabilities by different physicochemical tools
including physical properties (M.P), UV-Visible, IR and mass spectroscopy,
elemental and thermaogravimetric analyses. This search is aimed to adjust
suitable chemical environment for the preparation methodologies of above
mentioned metals with phthalocyanine ligand. These methods are take place
through different conditions using phthalic anhydride acid as starting
material.
2. Experimental and Results

2.1. Materials and reagents
44
All chemicals- reagents and solvents- used were of the analytical reagent
grade (AR), and of highest purity degree available, obtained from
commercial supplires. They included:
2.1.1. Solvents
2.1.1.1. N,N, dimethyl formamide (DMF), dimethylsulphoxide (DMSO),
Tetrahydrofuran (THF), ethanol, methanol, nitrobenzene, chloronaphthalene.
The solvents used for preparation and characterization were distilled before
use. All solvents were supplied from Middle East Company, Cairo, Egypt.
2.1.1.2. Water collected from a nanopure Milli-Q water purification system
of Millipore (Millipore Corp., Bedford, MA, USA) was used for all aqueous
solutions.
2.1.2. Chemicals
Phthalic anhydride, urea, ammonium molybdate, chromium chloride,
manganese(II) chloride tetrahydrate, iron(II) sulphate heptahydrate,
cobalt(II) chloride, nickel(II) chloride hexahydrate, copper(II) chloride
bentahydrate, sodium hydroxide, sulphuric acid, ammonia, sodium
methoxide. All reagents were used as received from suppliers.
2.2. Biological activity materials and preparations
2.2.1. Crystal violet and trypan blue dye, supplied from the Modern
Scientific Office Company, Cairo, Egypt.
2.2.2. DMEM, RPMI,-1640, FBS, HEPES buffer solution, from the Modern
Scientific Office Company, Cairo, Egypt.
2.2.3. L-glutamine, gentamycine and 0.25% Trypsin-EDTA, from the
Modern Scientific Office Company, Cairo, Egypt.
2.2.4. Tetracycline and Amphotericin were purchased from local markets.
2.2.5. Chloroform, dimethylsulphoxide ( DMSO ), supplied from Middle
East Company, Cairo, Egypt.
45
Distilled water was used for Standardization in antimicrobial tests.

2.3. Solutions
Stock solution of 1.0 M sodium hydroxide was prepared by dissolving the
accurately weighed amount in the appropriate volume of bidistilled water
and the volume completed to 1000 cm3 volumetric flask. Also, solution of 1
M hydrochloric acid was prepared by diluting accurate volume of the
concentrated stock acid in bidistilled water by using 1000 cm3 volumetric
flask.
2.4. Instruments
2.4.1. Infrared spectra of the ligand and its complexes were recorded in
potassium bromide discs (KBr) using FTIR-460 plus, JASCO, Japan, in
4000400 cm1 region in Central Laboratory, Cairo University, Cairo, Egypt.
2.4.2. The mass spectra measurements were recorded with the aid of a
SHIMADZU QP-2010 plus mass spectrometer at 70 eV at Al-Azhar
University, Cairo, Egypt.
2.4.3. The thermogravimetric analysis (TGA and DrTGA) was carried out in
dynamic nitrogen atmosphere (20 cm3 min1 ) with a heating rate of 10 C
min1 using SHIMADZU TGA-50H Thermal Gravimetric Analyzer, in the
Central Laboratory and in the Microanalytical Center, Cairo University
using DTG-60H SIMULTANEOUS DTA-TG APPARATUS-SHIMADZU in
dynamic nitrogen atmosphere ( 30 cm3 min1 ) with heating rate of 10 C
min1.
2.4.4. Spectrophotometric measurements were carried out using automated
spectrophotometer UVVis SHIMADZU Lambda 4B ranged from 200 to
900 nm and UVVis SHIMADZU 1800 using 1 cm matched quartz cells in
46
Centeral Laboratory and Microanalytical Center, Cairo University, Cairo,

Egypt.
2.4.5. Elemental microanalysis of the separated solid compounds of
phthalocyanine and metals with the Pc ligand, for C, H and N were
performed in the Microanalytical Centre, Cairo University using an
automatic CHN analyzer.
2.4.6. Magnetic susceptibility measurements were carried out at Central
Laboratory, Cairo University using Gouy magnetic balance consisting of
NP-53 type electromagnets with a dc power supply unit and a semimicro
electronic balance supplied by AND Electronics, Japan. Pascals constants
were used to calculate the diamagnetic corrections. A mercury
tetrathiocyanto cobaltate, Hg[Co(SCN)4], was used as calibration standard,
and doubly distilled water was used throughout the experiment.
2.5. Preparation of ligand (L) and its metal complexes
2.5.1. Preparation of Phthalocyanine (H2Pc) ligand (L)
The Phthalocyanine (Pc) ligand (Fig.1.1) was prepared by a reaction of
equimolar quantities of phthalonitrile and ammonia (0.002 mol) in refluxing
methanol solution (150 cm3) at around 120 C, 10 cm3 of sodium methoxide
was added, the reaction mixture was heated for 4-5 hours. Then cooled to
room temperature. 10 cm3 of water were added, the mixture was mixed
thoroughly, clear solution was removed by decantation and the dark greenblue precipitate was washed with ethanol, acetone, and dried in an oven for 6
hours at 60 C to yield ( 0.95 g) of product ( 85%).
2.5.2. Preparation of Metal Phthalocyanine complexes (MPc)
47
2.5.2.1. Preparation of Chromium (III) Phthalocyanine complex

(CrPc.Cl)
Chromium (III)chloride trihydrate salt ( 0.65g, 0.00307mol ), 1.82g
(0.0123mol) of phthalic anhydride, 4.243g (0.0707 mol) of urea and 0.15g of
ammonium molybdate were placed into a test-tube and heated in a sand-bath
to around 190-220C for 2-3 hours. The mixture was cooled to room
temperature. 10 cm3 of water were added, the mixture was mixed
thoroughly, clear solution was removed by decantation and residue was
boiled 2 hours, first with 150 cm3 of 1.0 M HCl and then with 150 cm3 of 1.0
M NaOH, filtered, and washed with distilled water each time until the
filtrate was neutral. The solid material was then stirred in methanol, suctionfiltered, and dried in an oven for 6 hours at 60 C .( The yield was 1. 60 g,
87.7% of theoretical yield ).
2.5.2.2. Preparation of Manganese (II) Phthalocyanine complex (MnPc)
0.35g (0.00177mol) of manganese(II) chloride (MnCl2.4H2O) were placed
into a round bottomed flask. The flask was flame-dried with the metal in it
until the water vapors were driven off. The flask was cooled to room
temperature, (1.047g, 0.0071mol) of Phthalic anhydride, 2.443g (0.0407mol)
of urea and 0.15g of ammonium molybdate were added. A dry reflux
condenser containing a drying tube at the top was added and the mixture was
brought to reflux on a sand bath at 190-220 C for 2-3 hours. Then the
mixture was cooled to room temperature. 10 cm3 of water were added, the
mixture was mixed thoroughly and filtered. The crude product was boiled 2
hours, first with 150 cm3 of 1.0 M HCl and then with 150 cm3 of 1.0 M
NaOH, filtered, and washed with water each time until the filtrate was
neutral. The solid material was then stirred in methanol, suction-filtered, and
48
dried in an oven 6 hours at 60 C .( The yield was 0.84 g, 83.6% of

theoretical yield).
2.5.2.3. Preparation of Iron (II) Phthalocyanine complex (FePc)
Phthalic anhydride (1.065 g, 0.007 mol), 2.48 g (0.0.041 mol) of urea, 0. 5 g
(0.002 mol) of Iron(II) sulphate heptahydrate (FeSO4.7H2O), and 0.15 g of
ammonium molybdate were suspended in 150 cm3 of nitrobenzene and
heated at 190 C. After gas evolution ceased (4-5 h), the mixture was filtered
hot and then washed with nitrobenzene, followed by methanol. The crude
product was then finally-as described above-purified with 1.0 M HC1
followed by 1.0 M NaOH: yield 0.839 g, 82.1% of theoretical yield.
2.5.2.4. Preparation of Cobalt (II) Phthalocyanine complex (CoPc)
phthalic anhydride (1.07 g, 0.007 mol), 2.49 g (0.042 mol) of urea, 0.23 g
(0.002 mol) of cobalt(II) chloride, and 0.2 g of ammonium molybdate were
suspended in 150 cm3 of nitrobenzene and heated at 190 C. After gas
evolution ceased (4-5 h), the mixture was filtered hot and then washed with
nitrobenzene, followed by methanol. The crude product was then finally-as
described above-purified with 1.0 M HC1 followed by 1.0 M NaOH: yield
0.89 g, 88.5% of theoretical yield.
2.5.2.5. Preparation of Nickel (II) Phthalocyanine complex (NiPc)
phthalic anhydride (1.171 g, 0.008 mol), 2.73 g (0.046 mol) of urea, 0.47 g
(0.002 mol) of nickel (II) chloride hexahydrate (NiCl2.6H2O), and 0.2 g of
ammonium molybdate were suspended in 150 cm3 of nitrobenzene and
heated at 190 C. After gas evolution ceased (4-5 h), the mixture was filtered
hot and then washed with nitrobenzene, followed by methanol. The crude
product was then finally-as described above-purified with 1.0 M HC1
followed by 1.0 M NaOH: yield 0.87 g, 77.3% of theoretical yield.
2.5.2.6. Preparation of Copper (II) Phthalocyanine complex (CuPc)
49
0.45g (0.002mol) of Copper(II) chloride pentahydrate (CuCl2.5H2O) were

placed into a watch glass, dried in an oven until the water vapors were
completely expelled. The resultant salt was placed into a mortar, 1.19g
( 0.008mol) of Phthalic anhydride, 2.78g (0.046mol) of urea and 0.1g of
ammonium molybdate were added, finely powdered with pestle and heated
in a test-tube in a sand-bath to around 190-220C for 2-3 hours.The crude
product was boiled 2 hours, first with 150 cm3 of 1.0 M HCl and then with
150 cm3 of 1.0 M NaOH, filtered, and washed with water each time until the
filtrate was neutral. The solid material was then stirred in methanol, suctionfiltered, and dried in an oven 6 hours at 60 C .( The yield was 1.05 g, 90.4%
of theoretical yield).
2.6. Analytical techniques
2.6.1. UV-Vis absorption
2.6.1.1 UV-Vis absorption spectrum of ligand (L)
The electronic spectrum of free ligand in pyridine was recorded in the
wavelength range 200 900 nm.
2.6.1.2. UV-Vis absorption spectra of complexes
The electronic spectra of 10-5 M of the studied complexes were scanned in
Dimethylsulphoxide (DMSO) and Dimethylformamide (DMF) in the
wavelength range 200 900 and 190 1100 nm.
2.6.2. Determination of the wavelengths of the maximum absorbance
(max)
Pthalocyanine solution 10-5 M was prepared by dissolving the accurately
weighed amount in the appropriate volume of pyridine using 10 cm3
measuring flask. 1cm3 of 10-5 M solution of standard phthalocyanine was
diluted by pyridine using 10 cm3 measuring flask. The absorption of resulted
50
solution (10-5 M) was scanned in the wavelength range 200 900 nm, to
determine the max of the ligand.
Metal phthalocyanine solutions were prepared and -as described abovescanned using DMSO as a solvent, then the wavelengths of the maximum
absorbance max of each complex solution was determined in the same
wavelength range.
2.7. Physical properties of phthalocyanine ligand and its metal
complexes
The physical properties of the solid free ligand and metal complexes were
studied (colour, M.P, solubility). The melting points of solid free ligand and
its metal complexes were investigated by using melting point apparatus.
Elemental analysis (C, H, N, and metal content) were made at the Micro
analytical Center of Cairo University using automatic CHN analyzer.
2.8. Spectroscopic studies of phthalocyanine ligand and its metal
complexes
The structures of the solid free ligand and its complexes were investigated
by using spectroscopic tools (IR and MS) together with thermal analysis
(TG and DTG).
2.8.1. IR Study of the ligand and its metal complexes
The Infrared spectra of the ligand and its metal complexes were recorded by
using FT-IR spectroscopy. The IR absorption spectra were taken in the range
of 4000-400 cm-1. Spectra were recorded with KBr pellet.
The solid sample of phthalocyanine ligand and metal complexes were
prepared by mixing a finely ground solid sample (0.5-1.0 mg) with
powdered potassium bromide by using a mechanical means, the mixture was
then pressed under high pressure (10,000-15,00 psi) until a clear pellet was
formed, the resulted pellet was inserted into a holder in the spectrometer, the
51
IR absorption was scanned in the range of 4000-400 cm-1 , to record the IR

absorption spectra of the studied compounds.
2.8.2. Thermal analysis Study of ligand and its metal complexes (TGA &
DTG)
The thermal analysis of the ligand and its metal complexes were made using
conventional thermal analyzers (Shimadzu system of DTA-50H and 30
series TG-50). These instruments were calibrated using indium metal as a
thermal stable material. The mass losses of identified weight of sample and
heat response of the change of the sample were measured from room
temperature up to 1000 C. The reproducibility of the instrument reading
was determined by repeating each experiment three times. The
thermogravimetric analysis (TGA and DTG) of the solid ligand and metal
complexes were carried out in dynamic nitrogen atmosphere (20 cm3 min-1)
and (30 cm3 min-1) with a heating rate of 10 C min-1.
2.8.3. MS Study of the ligand and its metal complexes
Electron ionization mass spectra were obtained using SHIMADZU QP-2010
plus and Shimadzu GCMS-QP 1000 EX quadrapoule mass spectrometer
with electron multiplier detector equipped with GCMS data system. The
direct probe for solid material was used in this study. The sample was put
into a glass sample micro vial by a needle (1 mg max.), the vial installed on
the tip of the DP containing heating cable and inserted into the evacuated ion
source. The sample was ionized by electron beam emitted from the filament,
the generated ions being effectively introduced into the analyzer by the
focusing and extractor lenses system. The MS was continuously scanned and
the spectra obtained were stored. Electron ionization mass spectra were
obtained at ionizing energy value of 70 eV, ionization current of 60A and
vacuum is better that 106 Torr.
52
2.9. Magnetic susceptibility

The magnetic susceptibility of metal complexes MPcs have been
investigated in the solid state at room temperature using Gouy magnetic
balance consisting of NP-53 type electromagnets with a dc power supply
unit and a semimicro electronic balance supplied by AND Electronics,
Japan. Pascals constants were used to calculate the diamagnetic corrections
A mercury tetrathiocyanto cobaltate, Hg[Co(SCN)4], was used as calibration
standard, and doubly distilled water was used throughout the experiment.
The mass susceptibility Xg of sample per gram was given by the following
expression:
X g=
CL
(RR )
m
... (1)
Where:
L: sample length (cm)
m: sample mass (gm), [ m = w2 - w1 (weight of tube plus sample weight of
empty tube) ]
C: proportionality constant (C = 2.086 x10-9)
R: reading obtained for tube plus sample
Ro: the empty tube reading (normally negative)
The molar susceptibility Xm is Xg multiplied by the molecular weight of the
substance, which is positive for the paramagnetic compound and negative
for diamagnetic one. For paramagnetic metal ion, the effective magnetic
moment, eff of the ion in Bohr magnetons (B.M.) and Xm are related by
the
expression:
53
( eeff ) =
3KT X m
N
(2)
Where,
N = Avogadro's number
= The Bohr magneton
K = Boltzmann's constant
T = absolute temperature (K)
Hence,
eff =2.84 ( X
T )
(3)
The diamagnetic correction were made by Pascals constant and

Hg[Co(SCN)4] was used as a calibrant.
2.10. Biological activity of the ligand and its metal complexes
2.10.1. Antimicrobial activity
The antibacterial and antifungal activities of the tested samples were carried
out in the Micro Analytical Center, Cairo University, Cairo, Egypt, using a
modified Kirby-Bauer disc diffusion method 232, under standard conditions
using MuellerHinton agar medium, as described by NCCLS 233.The
antimicrobial activities were carried out using culture of , Staphylococcus
aureus and Bacillus cereus as Gram-positive bacteria , Escherichia coli and
Pseudomonas aeruginosa as Gram-negative bacteria for antibacterial test,
and Aspergillus flavus and Candida albicans for antifungal test. Briefly, 100
dm3 of the test bacteria and fungi were grown in 10 cm3 of fresh media
until they reached a count of approximately 108 cells/cm3 and 105 cells/cm3
54
for bacteria and fungi respectively. 100 dm3 of microbial suspension was
spread onto agar plates corresponding to the broth in which they were
maintained, plates inoculated with tested filamentous fungi at 25 C for 48
hours; Gram-positive bacteria and Gram-negative bacteria they were
incubated at 35-37 C for 48 hours and, then the diameters of the
inhabitation zones were measured in millimeters, the diameter of the clear
zone of inhibition surrounding the sample is taken as a measure of the
inhibitory power of the sample against the particular test organism ( %
inhibition = sample inhibition zone (cm) / plate diameter x 100). DMSO (0.1
cm3) alone was used as control under the same conditions for each
microorganism, subtracting the diameter of inhibition zone resulting with
DMSO, from that obtained in each case. The results were compared with a
similar run of Tetracycline as an antibacterial and Amphotericin as
antifungal agents. The antimicrobial activities could be calculated as a mean
of three replicates 232.
2.10.2. Cell culture and cytotoxicity determination
Human hepatocellular Carcinoma (Hep-G2) cancer cell lines was used for in
vitro screening experiments; It was obtained frozen in liquid nitrogen ( -180
C ) from the American Type Culture Collection. The tumor cell was
maintained in the Regional Center for Mycology & Biotechnology, ALAzhar University, Cairo, Egypt, by serial sub-culturing. Cell culture
cytotoxicity assays were carried out as described previously.
The cell was propagated in Dulbeccos modified Eagles medium (DMEM)
supplemented with 10% heat-inactivated fetal bovine serum, 1% Lglutamine, HEPES buffer and 50g cm3 gentamycin. The cell was
maintained at 37 C in a humidified atmosphere with 5% CO2 and was
subcultured two times a week.
55
Cell toxicity was monitored by determining the effect of the test samples on
cell morphology and cell viability. Cell was seeded in 96-well plate at a cell
concentration of 1X 104 cells per well in 100 dm3 of growth medium. Fresh
medium containing different concentrations of the test sample was added
after 24 hours of seeding. Serial tow-fold dilutions of the tested chemical
compound were added to confluent cell monolayers dispensed into 96-well,
flat-bottomed microtiter plates (Falcon, NJ, USA) using a multichannel
pipette. The microtiter plates were incubated at 37 C in a humidified
incubator with 5% CO2 for a period of 48 hours; three wells were used for
each concentration of the test sample. Control cells were incubated without
test sample and with DMSO. The little percentage of DMSO present in the
wells (maximal 0.1%) was found not to affect the experiment. After
incubation of the cells for 24 hours at 37 C, various concentrations of
samples (50, 25, 12.5, 6.125, 3.125, 1.56 g) were added, and the incubation
was continued for 48 hours and viable cells yield was determined by a
colorimetric method.
After the end of the incubation period, media were aspirated and the crystal
violet solution (1%) was added to each well for at least 30 minutes. The stain
was removed and the plates were rinsed using tap water until all excess stain
is removed. Glacial acetic acid (30%) was then added to all wells and mixed
thoroughly, and then the absorbance of the plates were measured after gently
shaken on Microplate reader (TECAN, Inc.), using a test wavelength 0f 490
nm. All results were corrected for background absorbance detected in wells
without added stain. Treated samples were compared with the cell control in
the absence of the tested compounds. All experiments were carried out in
triplicate. The cell cytotoxic effect of each tested compound was calculated
234,235
.
56
2.11. Results
2.11.1. Preparation
The procedures used for the preparation of metal phthalocyanines resulted in
pure compounds and have a blue green colour for phthalocyanine ligand, a
dark blue for Cu (II), Ni (II) and Fe(II) complexes, blue-violet for Co (II)
complex, blue for Mn (II) complex and blue with a green tinge for Cr (III)
complex. The metal phthalocyanine complexes are thermally stable. These
complexes give a clear solution with concentrated sulfuric acid and are fairly
soluble in DMSO, DMF, CHCl3, THF, Toluene and pyridine but insoluble in
water and in most other common organic solvents like alcohol, ether, carbon
tetrachloride and benzene.
2.11.2. Spectrophotometric determination for selection of suitable
precursor
2.11.2.1. Wavelength (max) of phthalocyanine metal complexes
Two solutions of metal phthalocyanine prepared from phthalic acid and
phthalic anhydride respectively, were studied spectrophotometrically. The
solutions were scanned against dimethylsulphoxide (DMSO) as blank from
400 800 nm. The obtained absorption spectra showed that, the maximum
absorption of the examined solutions was due to the solution prepared from
phthalic anhydride acid.
2.11.3. UV-Vis spectra
UV-Vis spectroscopy is an excellent tool for phthalocyanine investigation
and characterization. The electronic spectral data for phthalocyanine ligand
and its metal complexes were recorded in the range 200900 nm and 190
1100 nm using pyridine as a solvent for (L), DMF for manganese complex
and DMSO for the other metal complexes. The UV-Vis spectra for 1X10-5 M
57
solutions of phthalocyanine and phthalocyanine metal complexes are shown

in Fig.2.(1 - 7).
2.11.3.1. Wavelength (max) of phthalocyanine ligand solution
Phthalocyanine ligand was studied spectrophotometrically. The reagent
solution was scanned against pyridine as blank from 200 900 nm (Fig.
2.1). The obtained absorption spectrum showed that, the maximum
absorption of the complex at max = 706 nm.
2.11.3.2. Wavelength (max) of chromium(III) phthalocyanine complex
Standard chromium(III) phthalocyanine solution was scanned
spectrophotometrically from 200 900 nm (Fig. 2.2), using
dimethylsulphoxide (DMSO) as blank. The absorption spectrum showed the
maximum absorption of the complex at max = 685 nm.
2.11.3.3. Wavelength (max) of Manganese(II) phthalocyanine complex
Standard manganese(II) phthalocyanine solution was scanned
dimethylformamiide (DMF) as blank. The absorption spectrum showed the
2.11.3.4. Wavelength (max) of Iron(II) phthalocyanine complex
Standard Iron(II) phthalocyanine solution was scanned
2.11.3.5. Wavelength (max) of cobalt(II) phthalocyanine complex
Standard cobalt(II) phthalocyanine solution was scanned
58
2.11.3.6. Wavelength (max) of Nickel(II) phthalocyanine complex

Standard nickel(II) phthalocyanine solution was scanned
2.11.3.7. Wavelength (max) of Copper(II) phthalocyanine complex
Standard copper(II) phthalocyanine solution was scanned
59
Fig. 2.1: UV-Vis spectrum of 10-5 M phthalocyanine (H2Pc) ligand
60
Fig. 2.2: UV-Vis spectrum of 1X10-5 M standard CrPc.Cl complex
61
Fig. 2.3: UV Vis spectrum of 1X10-5 M standard MnPc complex
62
Fig.2.4: UV-Vis spectrum of 110-5 M standard FePc complex
63
Fig.2.5: UV-Vis spectrum of 110-5 M standard CoPc complex
64
Fig.2.6: UV-Vis spectrum of 110-5 M standard NiPc complex
65
Fig. 2.7: UV-Vis spectrum of 1X10-5 M standard CuPc complex
2.11.4. Structural investigation of solid ligand and its metal complexes

66
Structure investigation is an important part of complexes studies due to the

need to identify low level impurities and degradation of complexes. The
phthalocyanine ligand and metal phthalocyanine complexes were prepared,
separated and their structures were elucidated. The first step in metal
complexes characterization is to establish the precise chemical identity.
Elemental analysis, spectroscopic techniques, such as IR and mass
spectrometry, in addition to thermal analysis (TG/DTG) are sensitive tools
for such purposes. Therefore, the structures of the selected ligand and metal
complexes (phthalocyanine and metal phthalocyanine (MPc), where [M =
Cr, Mn, Fe, Co, Ni, and Cu] were investigated by these analytical
techniques.
2.11.4.1. Elemental analysis of ligand L and metal complexes
Elemental analysis of the prepared ligand and its metal complexes are
performed. The results of elemental analysis for C, H, N, and metal content
of the studied compounds are tabulated in table 2.1. From these results, the
general formulae are determined and mol masses are calculated.
Table 2.1: Analytical and physical data of phthalocyanine ligand

and its metal complexes
67
Elemental analysis
MPc
CrPc.Cl
Colour,
(yield %)
<300
64.02,
64.17
2.42,
2.69
18.53,
18.71
8.31,
8.68
67.64,
67.73
2.78,
2.84
19.67,
19.75
9.56,
9.68
67.14,
67.57
2.63,
2.84
19.48,
19.71
9.86,
8.83
blue-violet
(88.5)
67.35,
67.26
2.91,
2.82
19.45,
19.61
9.89,
10.31
blue
(77.3)
66.88,
67.29
2.64,
2.82
19.71,
10.01,
10.28
dark blue
(90.4)
66.33,
66.72
2.68,
2.80
19.21,
19.45
(C32H16CrN8.Cl),
mole mass=599
(87.70)
(C32H16MnN8),
mole mass =567.48
FePc
(C32H16FeN8),
mole mass = 568.37
CoPc
(C32H16CoN8), mole
mass = 571.46
NiPc
(C32H16NiN8), mole
mass = 571.22
CuPc
(C32H16CuN8), mole
mass = 576.08
Found (calcd %)
C
blue with
green tinge
MnPc
M.P
(o C)
blue
(83.60)
blue
(82.1)
19.62
10.92,
11.03
M = Cr(III), Mn(II), Fe(III), Co(II), Ni(II), and Cu(II), Pc = Phthalocyanine ligand

(C32H18N8), mole mass = 514.54 g. mol-1),(blue green)
2.11.4.2. IR spectral studies
68
Infrared (IR) spectroscopy is one of the most common spectroscopic

techniques used by organic and inorganic chemists. Simply, it is the
absorption measurement of different IR frequencies by a sample positioned
in the path of an IR beam. The main goal of IR spectroscopic analysis is to
determine the chemical functional groups in the sample. Different functional
groups absorb characteristic frequencies of IR radiation. Using various
sampling accessories, IR spectrometers can accept a wide range of sample
types such as gases, liquids, and solids. Thus, IR spectroscopy is an
important and popular tool for structural elucidation and compound
identification. To achieve an idea about the groups shared in formation of the
solid ligand, the IR spectra were compared with those of the metal
complexes under study 211.
IR spectral data of title complexes were recorded in KBr pellets and the
results are tabulated in Table 2.2, and the spectra are given in Fig. 2. (8-14).
Table 2.2: IR characteristic peaks of metal phthalocyanine complexes

Ligand and its metal complexes
69
Characteristi
c peaks
( cm-1)
Pc
OH in H2O
3420s
(NH)
3281s
CrPc
MnPc
3431s
3431s
FePc
CoPc
NiPc
CuPc
3433s
3421s
3431s
3049
3050
3047w
3049w
3050w
1611
1610
1610m
1612m
1616m
1520
1520s
1522s
1520w
1520w
1470
1505w
stretching
vibration
(CH)
3049w
3050w
symmetric
stretching
vibration
in ring
(CC)
1605m
1611m
stret
-ching
vibration
in pyrrole
(CH)
aryl
(CH) in
plane
1519m
1520w
1500w
1470w
1470w
1450w
1450m
w
1503
m
1450s
bending
m
1468
1472w
1498w
1472w
1460w
1450w
1500w
1457w
w
1460
w
(CC) in
isoindole
1438w
1432s
1417
1332vs
70
1430
1425s
1429w
1423w
1329s
1331v
1332vs 1332vs
1330vs
1288m
1290m
1289m
1164m
1165m
1162m
s
(CN) in
1296s
1289m
isoindole
(CN) in
1163m
1160m
plane
(CH)
1284
1288
1163
1160
1117s
1119s
1070v
1126s
1114s
ben -ding
1121vs 1121vs
1115s
1080s
1091s
1089vs
1088s
in plane
(CH) in
1045vs
1072vs
plane
deformatio
n
NH
1010vs
911w
910w
914w
916w
867m
896m
869w
870m
891m
bending
vibration
(CH)
out of
Plane
deformation
(CH)
out of
plane
defor
mation
71
(CN)
783w
777m
725vs
724vs
723vs
730s
779m
779m
729vs
721vs
stretching
vibration
(CH)
out of
plane
730vs
deformatio
n
w: weak, vs: very strong, s: strong, m: medium, sh: shoulder
72
Fig. 2.8: IR spectra of solid Pc ligand
73
Fig. 2.9: IR spectra of solid CrPc.Cl complex
74
Fig. 2.10: IR spectra of solid MnPc complex
75
Fig. 2.11: IR spectra of solid FePc complex
76
Fig. 2.12: IR spectra of solid CoPc complex
77
Fig. 2.13: IR spectra of solid NiPc complex
78
Fig. 2.14: IR spectra of solid CuPc complex
2.11.4.3. Thermal analysis and mass spectra

The fragmentation in both MS and TA techniques are similar where the
rupture takes place at the weakest bond positions 215. In TA, the molecules
are continuously energized and deactivated by a gas evolution and the
79
distribution of energy can be described as a function of temperature. In MS,

the ion produced is formed with a specific amount of internal energy, which
is conserved independently in all subsequent dissociations. During
ionization process, transitions to various states are possible leading to a
collection of ions with a distribution of internal energies. The dissociation
does not immediately follow ionization, but it is slow enough to permit the
transfer of energy into the various degrees of freedom involved in the
observed dissociation.
Thermogravimetric (TG/DTG) analysis is employed to provide quantitative
information on weight losses due to decomposition and/or evaporation of
low molecular material as a function of time and temperature. The particular
problem in studying TA of large molecule is that the decomposition takes
place in a series of overlapping reactions with multiple products.
Thermogravimetric curves for phthalocyanine and its metal complexes are
shown in Fig. [2. (1521)]. And the thermal analysis data are shown in Table
2.3.
Table 2.3: Thermal properties of phthalocyanine and

its complexes
80
Compound
Minor
Major
temperatur
temperature/
e/C
Pc
405
620
CrPc
360
605
MnPc
380
490
FePc
400
530
CoPc
370
455
NiPc
390
485
CuPc
395
610
81
Fig. 2.15: Thermal analysis of solid Pc ligand:
a-
TG/DTG
82
Fig. 2.16 ( a-b): Thermal analysis of CrPc.Cl:

a- TG
b- TG/DTG
83
Fig. 2.17 (a b): Thermal analysis of MnPc:

a- TG
b- TG/DTG
84
Fig. 2.18: Thermal analysis of FePc:

TG/DTG
85
Fig. 2.19: Thermal analysis of CoPc:

a- TG
b- TG/DTG
86
Fig. 2.20: Thermal analysis of NiPc:

a- TG
b- TG/DTG
87
Fig. 2.21: Thermal analysis of CuPc:

a- TG
b- TG/DTG
88
2.11.4.4. Mass spectra of phthalocyanine and metal complexes

2.11.4.4.1. Mass spectrum of phthalocyanine ligand
The MS spectrum of phthalocyanine ligand is shown in Fig.
2.22.
Fig. 2.22: Mass spectra of Pc (L)
This mass spectrum is characterized by many competitive and consecutive

pathways, thus forming many intense fragment ions. The base peak in
the spectrum appears at m/z= 514 may be due to the
molecular ion [C32H18N8]. The main molecular ion thermally
decomposed leading the formation of fragment ions
[ C16N3H6]+, [C8N3H3]+, [C8N2H3]+ observed in the mass spectra
at m/z= 240, 141 and 127 respectively. The peak in the
spectrum that appears at m/z= 27 may be due to the
89
formation of HCN gas as a result of formation of [HCN] +

fragment ion as shown in Scheme 2.1. Other important
fragment ions are appeared at m/z= 103 and at m/z= 51,
respectively. These fragment ions may be due to the
formation of [C7H5N]+ and [C4H3]+, respectively.
N
N
H
H
N
N
N
N
(I)
(II)
(III)
90
N
CN
-e, H
C 8N 3H4+ -e, H
(142)
NH +
(15)
CN
(127)
e
-2
(I)
C 4H 3
2H
(129)
(51)
-CN
(103)
-e
C 4N 3
(90)
C 6H 4+
(76)
HCN+
(27)
CN
N
-NH3, 4H
-e
(114)
CN
(127)
(II)
CN
CN
(103)
N
N
-e, H
2H
(241)
(243)
-e
2H
-e
(III)
(243)
-N
,H
(230)
C16N3H6 +
(240)
)
-5
=1
(n
H N2
-n - H
(206)
91
C9N 2H3+
(139)
C7NH6+
(104)
Scheme 2.1: Mass fragmentation pathways of Pc ligand
2.11.4.4.2. Mass spectrum of Chromium phthalocyanine complex

The MS spectrum of Chromium phthalocyanine complex is
shown in Fig. 2.23.
Fig. 2.23: Mass spectra of CrPc.Cl

The base peak in the spectrum appears at m/z= 564 may be due to the
molecular ion [C32H16CrN8]. The peaks appear at m/z= 292, 141 and 127, may
be due to the formation of fragment ions [ C16N3H6Cr]+, [C8N3H3]+,
[C8N2H3 ]+ as shown in Scheme 2.2. The signals appear at m/z = 240 and 142
respectively, these fragment ions may be due to the formation of [C16N3H6]+,
[C8N3H4]+.
92
N
N
Cr
N
N
N
N
N
(I)
(II)
(III)
93
Cr
(43)
N,
2H
(29)
CN
-e, H
C 8N 3H4+ -e, H
(142)
NH +
(15)
CN
(127)
(I)
nH
(n
=3
)
(130)
CN
CN
-NH3, nH
(n=1-5)
-e
CN
(103)
(127)
2H
(II)
(105)
N
,H
NH
(134),(135)
N
N
N
Cr
-e, H
(293)
-H, 2CN
e
-2
(III)
Cr
(52)
C16N3H6 +
(240)
)
-5
=1
(n
H N2
-n -H
(206)
94
(344)
(119)
Scheme 2.2: Mass fragmentation pathways of CrPc.Cl complex
2.11.4.4.3. Mass spectrum of Manganese phthalocyanine complex

The MS spectrum of Manganese phthalocyanine complex is
shown in Fig. 2.24.
Fig. 2.24: Mass spectra of MnPc

The base peak in the spectrum appears at m/z= 567 may be due to the
molecular ion [C32H16MnN8]+. The signals that appear at m/z= 295, 141 and
127 may be due to the formation fragment ions [C16H6N3Ni], [C8H3N3]+ and
[C8H3N2]+ as shown in Scheme 2.3. The signal appears at m/z = 128 is may
be due to the fragment [C8H4N2]. The peaks appear at m/z =284 is attributed
mainly to the loss of nitrogen and hydrogen from fragment ion [C16H6N4Ni]
95
leading to form the fragment ion [C16H9N2Mn]+ . The peak appear at m/z =
27 is due to the formation of fragment ions [HCN]+.
N
N
N
Mn
N
N
96
N
N
N
Mn
(II)
(I)
(III)
N
CN
N
-N, H
(129)
-CN
(103)
-e
CN
(128)
(I)
HCN+
(27)
N
,3
H
C6H 4+
(76)
(44)
CN
N
-e
-e
CN
C2N 2+
(52)
H
,6
H2
C6
(127)
(II)
C6H3+
(75)
(155)
97
N
N
N
Mn
-e, H
(296)
e
-2
-N
,2
H
(284)
(III)
Mn
(55)
C16N3H6 +
(240)
)
-4
=1
(n
H N2
-n -H
(208)
Scheme 2.3: Mass fragmentation pathways of MnPc complex
2.11.4.4.4. Mass spectrum of Iron phthalocyanine complex

The MS spectrum of iron phthalocyanine complex is shown in
Fig. 2.25.
98
Fig. 2.25: Mass spectra of FePc
The signal that appears at m/z = 568 refers to the appearance of the
molecular ion (C32H16FeN8). The signal appears at m/z = 284 is attributed
mainly to the loss of nitrogen from the fragment ion (C16H6N3Fe).The signal
that appears m/z = 240, at m/z = 142 and at m/z= 127, these fragment ions
may be due to the formation of [C16N3H6]+, [C8N3H4]+and [C8N2H3]+ ,
respectively.
99
N
N
Fe
N
N
N
N
N
Fe
(II)
(I)
(III)
N
CN
N
-e, H
C8N3H4
(142)
-e, H
NH +
(15)
CN
(127)
(I)
nH
( n=
12)
(128),(129)
100
CN
CN
(110),(112),(113),(114),(115)
,2
H2
-N
-NH3, nH
(n=1-5)
-e
(127)
(II)
(92)
N
N
N
-N, 2H
Fe
(284)
e
-2
(III)
Fe
(56)
C16N3H6 +
(240)
)
4
1=
(n
H N2
-n -H
(207),(208),(209)
Scheme 2.4: Mass fragmentation pathways of FePc complex
101
2.11.4.4.5. Mass spectrum of Cobalt phthalocyanine complex

The MS spectrum of cobalt phthalocyanine complex is shown
in Fig. 2.26.
Fig. 2.26: Mass spectra of CoPc
The signal that appears at m/z= 571 may be due to the molecular ion
[C32H16CoN8]+. The moderate intensity reflects the stability of the molecular
ion of cobalt phthalocyanine complex following EI. The base peak in the
spectrum that appears at m/z= 59 may be due to the formation of Co as a
result of fragmentation [C16H6N3Co] ion as shown in Scheme 2.5. The signal
appears at m/z = 100 is attributed mainly to the loss of fragment ion CN
102
from the entity of [C8H3N2]+ ion leading to the formation of [C7H4N]+ . Other
important fragment ions are appeared at m/z = 240, at m/z = 142 and at m/z=
127, respectively, these fragment ions may be due to the formation of
[C16N3H6]+, [C8N3H4]+and [C8N2H3]+ .
103
N
N
Co
N
N
N
N
N
Co
(II)
(I)
(III)
N
CN
N
-e, H
C8N3H4
(142)
-e, H
NH
CN
(127)
(I)
nH
(
n=
1-4
)
(128),(129),(130),(131
)
104
CN
N
-NH3, nH
(n=1-5)
-e
(110),(112),(113),(114),(115)
H
,n
H2 )
-N =1-2
(n
CN
(127)
(II)
(95),(96),(97)
CN
CN
N,
nH
(n =
1
-4 )
(117),(119)
N
N
N
Co
-e, H
(300)
Co
(59)
(351)
-N
e
-2
(III)
-H, 2CN
(286)
C16N3H6 +
(240)
)
-4
=1
(n
H N2
-n -H
(207)
Scheme 2.5: Mass fragmentation pathways of CoPc complex
105
2.11.4.4.6. Mass spectrum of Nickel phthalocyanine complex

The MS spectrum of Nickel phthalocyanine complex is shown
in Fig. 2.27.
Fig. 2.27: Mass spectra of NiPc
This spectrum is helpful in the interpretation of the formation of some

fragment ions in the present mass spectrum. The signal that appears at m/z=
570 refers to the appearance of the molecular ion [C32H16NiN8]+. The moderate
intensity reflects the stability of the molecular ion of NiPc complex
following EI. The peaks that appears at m/z= 298, 141, 127 are due to the
main fragmentation of the molecular ion giving the fragments [C16N3H6Ni],
106
[C8N3H3] and [C8N2H3]. The base peak in the spectrum that appears at m/z=
254 is mainly due to a formation of [C16H6N4] ion as secondary process as
shown in Scheme 2.6; the m/z= 254, other important ions are observed in the
mass spectra at m/z = 240, at m/z = 142 and at m/z= 127, respectively. These
fragment ions may be due to the formation of [C16N3H6]+, [C8N3H4]+ and
[C8N2H3]+ .
107
N
N
Ni
N
N
N
N
N
Ni
(II)
(I)
(III)
-2e
C 4H 3
C4N3
(51)
(90)
(I)
-e, H
C8N 3H 4+
(142)
108
nH,(n=1-5)
(91),(92),(93),(94),(95)
CN
-e
NH
CN
(127)
- NH
(n = 3, nH
1-5
)
(II)
(110),(112),(113),(114),(115)
H
,n
H2 )
-N =1-2
(n
(95),(96),(97)
-e, H
(255)
-2e, H
2 C6H3+
C4N4+
(75)
(104)
)
-3
=1
,(n
nH
(105),(106),(107)
N
N
-e, H
Ni
(299)
e
-2
(III)
Ni
(58)
-H, 2CN
(250)
-N
(285)
C16N 3H6 +
(240)
)
4
1=
(n
2
H N
-n -H
(208)
Scheme 2.6: Mass fragmentation pathways of NiPc complex
109
2.11.4.4.7. Mass spectrum of Copper phthalocyanine complex

The MS spectrum of Copper phthalocyanine complex is
shown in Fig. 2.28.
Fig. 2.28: Mass spectra of CuPc
The careful inspection of MS of copper phthalocyanine complex, main

molecular ion of this compound is difficulty detected with very low intensity
(at m/z = 576), which may be due to the high thermal stability of the
molecular ion of copper phthalocyanine complex, the later may be due to its
higher bonding energy .
The peak that appears at m/z = 303 is mainly due to a formation of fragment
ion [C16H5N3Cu] due to rupture of [C32H16CuN8] (mol mass=576) as shown
in Scheme 2.7, also another two peaks which appear at m/z = 141 and 127
are due to the formation of fragments ions of [C8H3N3] and [C8H3N2]
respectively, these peaks are due to rupture of the previous ion in the same
pattern. Other important fragment ions are observed in the mass spectra at
m/z = 240, at m/z = 142 and at m/z= 127, respectively. These fragment ions
110
may be due to the formation of [C16N3H6]+, [C8N3H4]+and [C8N2H3]+ ,

respectively.
N
N
Cu
N
N
N
N
N
Cu
(II)
(I)
(III)
CN
N
-e, H
C 8N 3H4+ -e, H
(142)
NH +
(15)
CN
(127)
(I)
nH
( n=
3)
(130)
111
(29)
CN
N
(110),(112),(113),(114),(115)
CN
(127)
(II)
(95),(96),(97)
N
N
N
Cu
-e, H
Cu
(63)
-H, 2CN
(304)
(355)
-N
e
-2
(III)
H
,n
H2 )
-N =1-2
(n
-NH3, nH
(n=1-5)
-e
(290)
C16N3H6 +
(240)
)
-4
=1
(n
H N2
-n -H
(207)
Scheme 2.7: Mass fragmentation pathways of CuPc complex
112
2.11.5. Magnetic susceptibility

The magnetic susceptibility Xm, and magnetic moments eff values of MPcs
have been investigated in the solid state and the results are summarized in
Table 2.4. The values reported in the Table are the average of the three
independent determinations.
Table 2.4: Magnetic susceptibility and magnetic moments values of
metal phthalocyanine complexes
MPc
Magnetic
Susceptibility
( X g x10-6 cgs
units)
Magnetic
susceptibility
( X m x10-6 cgs
units )
CrPc
0.209
12544
4.75
MnPc
0.185
10520.5
4.35
FePc
0.149
8456
3.90
CoPc
4.2
4113.3
2.72
NiPc
9.10
5200.4
CuPc
3.99
2299
1.73
113
effe (B.M)
2.11.6. Biological activity studies

2.11.6.1. Antimicrobial activity
The data in table 2.5, showed that the ligand (L) and its complexes have the
capacity of inhibiting the metabolic growth of the investigated
microorganism, S. aureus, and B. cereus as Gram-positive bacteria and E.
coli and P. aeruginosa as Gram-negative bacteria, Aspergillus flavus and
Candida albicans as fungi, to different extents. The size of the inhibition
zone depends upon the culture medium, incubation conditions, rate of
diffusion and the concentration of the antimicrobial agent (the activity
increases as the concentration increases).
The antimicrobial activities of ligand (L) and metal complexes (MPcs) are
shown in Fig. (2.29 -2.40).
2.11.6.2. Antitumor activity
To evaluate the potential usefulness of phthalocyanine metal complexes
prepared as antitumor agents, human heptacellular Carcinoma (Hep-G2) was
treated. All the studied compounds showed activity against the studied cell
line, table (2.6 - 2.12).
The inhibitory activity against heptacellular Carcinoma cells are shown in
Fig. (2.41- 2.47).
114
Table 2.5: The anti bacterial and antifungal activities

of the tested compounds
Gram
Microorganism
stain
Inhibition zone diameter (mm/mg

sample)
reactio
Compound code
n
C1
Escherichia coli
Pseudomonas
aeruginosa
Staphylococcus
aureus
negativ
e
C2
C3
12
12
12
12
10
16
20
0.0
13
0.0
14
11
10
12
13
11
10
14
11
18
10
10
10
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
negativ
e
positiv
e
Bacillus cereus
positiv
e
Aspergillus flavus
fungus
Candida albicans
fungus
115
116
Fig. 2.29: Antibacterial activity of studied samples
117
118
Fig. 2.31: Antifungal activity of studied samples
119
120
121
122
123
124
125
126
127
128
Table 2.6: The Inhibitory activity of CrPc complex

against Hepatocellular carcinoma cells (IC50=37.3 g)
Sample conc.
Viability %
(g)
50
43.83
25
55.94
12.5
68.76
6.25
89.12
3.125
97.42
1.56
100
100
Table 2.7: The Inhibitory activity of MnPc complex

Sample conc. (g)
Viability %
50
33.58
25
47.60
12.5
70.38
6.25
86.52
3.125
95.82
1.56
100
129
100
Fig. 2.41: Inhibitory activity of CrPc complex
130
Fig. 2.42: Inhibitory activity of MnPc complex

Table 2.8: The Inhibitory activity of FePc against
Hepatocellular carcinoma cells (IC50=13.8 g)
Sample conc. (g)
Viability %
50
19.62
25
32.42
12.5
52.14
6.25
71.48
3.125
86.25
1.56
97.18
100
131
Table 2.9: The Inhibitory activity of CoPc complex

Sample conc. (g)
Viability %
50
23.96
25
36.84
12.5
59.40
6.25
78.36
3.125
90.14
1.56
98.92
100
Fig. 2.43: Inhibitory activity of Fe

132
Fig. 2.44: Inhibitory activity of CoPc complex

Table 2.10: The Inhibitory activity of NiPc complex
Sample conc. (g)
Viability %
50
47.12
25
59.26
12.5
71.58
6.25
83.13
3.125
95.86
1.56
98.92
100
133
Table 2.11: The Inhibitory activity of CuPc complex

Sample conc. (g)
Viability %
50
37.48
25
49.82
12.5
69.18
6.25
84.92
3.125
96.14
1.56
100
100
134
Fig. 2.45: Inhibitory activity of NiPc complex
Fig. 2.46: Inhibitory activity of CuPc complex

Table
2.12:
The
Inhibitory
activity
of
Hepatocellular carcinoma cells (IC50=37.5 g)

Sample conc. (g)
Viability %
50
42.90
25
57.12
12.5
69.78
6.25
90.36
3.125
98.15
1.56
100
135
against
100
Fig. 2.47: Inhibitory activity of L

3. Discussion and Conclusions
The phthalocyanine ligand and its metal complexes MPcs (M= Cr, Mn, Cu,
Fe, Co and Ni) have been prepared in the pure state with high yields. The
first three complexes were prepared in dry conditions without using any
solvent. These complexes have been characterized using elemental analysis,
UVVis, FT-IR, MS spectroscopy, and Thermogravimetric analytical
studies. Magnetic moments of these complexes were calculated from their
magnetic susceptibility values. The antimicrobial and antitumor activities
have also been studied.
3.1. UV-Vis spectra
136
The studied complexes showed a major Q-band absorption around 665680

nm and a shoulder like absorption around 595620 nm, Fig 2.(1 - 7).
Interpretation of the spectra is possible by using the analogy of the 18
-electron configuration of the porphyrin system 236. The deep bluish to
greenish colour of the complexes are due to the absorption peaks in the Q
band region 237. A small shoulder peak observed at lower wavelengths than
the main Q-band are additional components of the Q-band resulting from
either vibronic fine structure or dimeric species in solution 238. Coordination
of a metal to the phthalocyanine ring, compared to free base phthalocyanine,
shifts the Q-band to shorter wavelengths. This is due to the interaction
between the d-orbital of the metal and the phthalocyanine, i.e. strong metal
to ligand back-bonding 239. This interaction increases the separation
between the phthalocyanine HOMO and LUMO orbitals. The peaks
obtained in the B-band region are around 275295 nm. The broad absorption
peaks observed around 425450 nm may be due to the C4 symmetry of the
complexes 240.
3.2. Elemental analysis
The results of elemental analysis for carbon, hydrogen, nitrogen and metal
showed in table (2.1),) are in good agreement with the calculated values and
are consistent with the proposed structure (Fig. 1.1).
3.3. Infrared spectroscopy
From figures 2.(8 - 14) and Table 2.2, it can be observed that, the band
appearing about 3421-3431 cm-1 in the infrared spectra of phthalocyanine
and its complexes was assigned as an OH vibration of adsorbed water. The
NH stretching and bending vibrations were observed at about 3281 and 1010
cm-1, respectively in phthalocyanine. These bands disappeared in the infrared
137
spectra of phthalocyanine complexes. The absence of these bands in the

complexes is due to the replacement of hydrogen by metal cation. Two
bands appearing at about and 30482 cm-1 are assigned as CH asymmetric
and symmetric stretching vibrations in the ring, and those at 29234 and
2850 cm-1 are assigned as the CH symmetric and asymmetric stretching
vibrations as alkyl. The band appearing at 1610 6 cm-1 was assigned to the
CC stretching vibration in pyrrole and those at 14299 and 13325 cm-1
were assigned to CC stretching in isoindole. The two bands appearing at
1470 2 and 14555 cm-1 were assigned to the CH in plane bending
vibration and those at 15175, 149811 and 14746 cm-1 were assigned to
the CH bending in aryl. The two bands appearing at 11184 and 10856
cm-1 were assigned to CH bending in plane deformations. Also, the two
bands appearing at 9097, 88210 and 728 5 cm-1 were assigned to CH
bending out of plane deformations. The bands appearing at 12846, 11623
and 107011 cm-1 were assigned to the CN in isoindole in plane band in
pyrrole stretching vibration, respectively. Normal MPc show three strong
peaks in the 1000 1200 cm-1 region. The spectral pattern in this region
depends strongly on the molecular structure of the complexes and its
chemical structure for the central metal.
3.4. Thermogravimetric analysis (TGA)
All MPcs have been studied thermogravimetrically in the
atmosphere of nitrogen up to 1000 o C. All these complexes
showed exceptional thermal stability. The data revealed that all
complexes are stable up to 350 o C and show weight loss in
the temperature range of 350920 o C and the char yields are
found to vary depending on MPc. Thermogravimetric curves for
phthalocyanine and its complexes are shown in Fig. 2(15-21). The loss of
138
weight was attributed to the actual pyrolysis by a minor decomposition

reaction at about 405, 360, 380, 400, 370, 390 and 395 C and a major
decomposition reaction at 620, 605, 490, 530, 455, 485 and 610 C for Pc,
CrPc, Mn Pc, FePc, CoPc, NiPc and CuPc, respectively. Generally, the metal
complexes need thermal energy less than that of ligand and this because the
weaker bonding force between the metal and ligand. These results are
summarized in Table 2.3. The loss of weight at the major decomposition
temperature was 85% for Pc and 70% for CrPc.Cl, 77% for MnPc, 90% for
FePc, 89% for CoPc, 89% NiPc and 85% for CuPc.
3.5. Mass spectrometry
The mass spectra of the ligand L and its complexes, Fig. 2(22
- 28), were recorded at 70 eV. The phthalocyanine L has a
strong molecular ion peak at m/z 514, and decomposes to
offer peaks at m/z 240, 141 and 127, which is assigned to
the molecular ions [ C16N3H6]+, [C8N3H3]+ and [C8N2H3]+ respectively.
The fragment at m/z 27 is recognized to the molecular ion
[HCN]+, while that at m/z 103 is known to the molecular ion
[C7H5N]+ . The mass spectrum of M-L complex has M+ at m/z
corresponding to the molecular mass of [MPc] for the
complexes with three fragmentation molecular ions as shown
in Scheme ( 3.1 - 3.7 ).
3.6. Magnetic susceptibility
The magnetic susceptibility measurements of studied metal
phthalocyanines complexes were investigated in solid state
and the results are summarized in Table 2.4. The reported
values are the averages of the three independent
139
determinations. Experimental values revealed that the only

diamagnetic complex is the nickel one. The obtained results
could give indication for the coordination environment of the
metal centre and support the proposed electronic structure
of the complexes.
3.7. Biological activity studies
3.7.1. Antimicrobial activity
The data in table 2.5 showed that the tested samples have
antibacterial activity on the tested microorganisms. The
metal complexes have the capacity of inhibiting the
metabolic growth of the investigated bacteria,
Staphylococcus aureus and Bacillus cereus as Gram-positive
bacteria and Escherichia coli and Pseudomonas aeruginosa
as Gram-negative bacteria, Candida albicans as fungi, to
different extents. The size of the inhibition zone depends
upon the culture medium, incubation conditions, rate of
diffusion and the concentration of the antimicrobial agent
(the activity increases as the concentration increases). In the
present study, the MPc complexes are active against both
types of the bacteria, which may indicate broad-spectrum
properties. The remarkable activity of these compounds may
be arising from the isoindole ring, which may play an
important role in the antimicrobial activity. The mode of
action may involve the formation of a hydrogen bond
through the tertiary nitrogen of the isoindole ring with the
140
active centers of the cell constituents, resulting in

interference with the normal cell process.
The complexes of cobalt and copper are clearly active
against all the tested microorganisms except Aspergillus
flavus. At the same time, manganese complex exhibited high
antimicrobial activity against gram positive bacteria Bacillus
cereus reaching 18 mm clear zone and 20 mm against gram
negative bacteria Pseudomonas aeruginosa while other
compounds showed some antibacterial activity with
different extents. With respect to Candida albicans nickel
complex is the most active against this fungus. These results
are of great value to biological applications.
A possible explanation for the poor activity of these
complexes with respect to the reference antibiotic may be
attributed to their inability to chelate metals essential for the
metabolism of microorganisms and/or to form hydrogen
bonds with the active centers of cell structures, resulting in
an interference with the normal cell cycle. Furthermore, the
low activity of these complexes may be also due to their low
lipophilicity, because of which penetration of the complex
through the lipid membrane was decreased and hence, they
could neither block nor inhibit the growth of the
microorganism. Therefore, we confirm that the toxicity of the
complexes can be related to the strengths of the ML bond,
in addition to other factors such as size of the cation and
receptor sites.
141
3.7.2. Antitumor activity

To evaluate the potential usefulness of metal phthalocyanine
complexes prepared as antitumor agents, human
heptacellular Carcinoma (Hep-G2) was treated. All the
studied compounds showed activity against the studied cell
line. On screening, it was found that the iron complex is the
most active against the studied cell at 100 dm 3 with
IC50=13.8 g (IC50, compound concentration required to
inhibit tumor cell proliferation by 50 %) as shown in Fig. 3.43.
While the other complexes showed some antitumor activity
with different extents.
142
Recommendation
- Further work on phthalocyanine metals chelates should be done including
heavy metals.
- Substituted metal phthalocyanines could be prepared by introducing a
variety of functional groups in the peripheral positions to enhance the
solubility of these metal complexes in order to increase the area of their
applications.
- The studied complexes may be screened for their antiviral and antiinflammatory.
143
References
[1] I. Manners. Polymer science with transition metals and
main group elements: towards functional, supramolecular
inorganic polymeric materials. J Polym.Sci, Part A:
Polym.Chem;40, 17991, (2002).
[2] GR. Whittell, I. Manners. Metallopolymers: new
multifunctional materials. Adv Mater;19, 343968, (2007).
[3] ACW. Leung, MJ. MacLachlan. Schiff base complexes in
macromolecules. J Inorg. Organomet. Polym. Mater.;17: 57
89, (2007).
[4] KA. Williams, AJ. Boydston, CW. Bielawski.Main-chain
organometallic
polymers: synthetic strategies, applications, and
perspectives. Chem. Soc. Rev.;36, 72944, (2007).
[5] RJ. Puddephatt. Advances in organometallic polymers,
ring-opening
144
polymerization and the self-assembly of supramolecular

polymers. J Inorg. Organomet. Polym. Mater.;15, 37188,
(2005).
[6] WK. Chan. Metal containing polymers with heterocyclic
rigid main
Chains, Coord. Chem. Rev; 251, 210418, (2007).
[7] W.Y. Wong, Ho C.L. Di-, oligo-, and polymetallaynes:
Synthesis,
photophysics, structures and applications, Coord. Chem. Rev;
250, 262790, (2006).
[8] W.Y. Wong, Luminescent organometallic
poly(aryleneethynylene)s: functional properties towards
implications in molecular optoelectronics, Dalton Trans;
4495510, (2007).
[9] T. Yamamoto, H. Fukumoto, T. Koizumi. Metal complexes
of -conjugated polymers. J Inorg Organomet Polym
Mater;19, 311, (2009).
[10] AS. Abd-El-Aziz, Carraher Jr CE, Pittman Jr CU, M. Zeldin
Macromolecules containing metal and metal-like elements.
Wiley-Interscience, John Wiley & Sons, Inc ; New York, (2003
2007).
[11] F.H. Moser, A.L. Thomas, Phthalocyanines Compounds
, Rehinhold
Publishing Corporation, New York, (1963).
[12] C.C. Leznoff, A.B.P. Lever, Phthalocyanines, Properties
and
145
Applications , vol. 1, VCH Publications, Inc; New York,

(1989).
[13] J. Ikhal, L.R. Fulkner, K. Dwarakanath, K. Tachikawa, J.
Am. Chem.
Soc; 108, 5434, (1986).
[14] M. Phillipe, L. Regean, Van-Lier, E. John, Gasperd, J.
Photochem.
Photobiol.; B 14 (3), 187, (1992).
[15] P. Gregory, J. Porphyrins, Phthalocyanines; 4, 432,
(2000).
[16] C.C. Leznoff, A.B.P. Lever (Editors.), The
Phthalocyanines: Properties and Applications , vols. 14,
John Wiley and Sons Inc; New York, (19861993).
[17] N.B. Mckeown, Phthalocyanine Materials: Synthesis,
Structure, and
Function , Cambridge Univ. Press, Cambridge, (1998).
[18] F.H. Moser, A.L. Thomas, The Phthalocyanines , vols.
12, CRC
Press; FL, (1983).
[19] C.E. Dent, R.P. linstead , A.R. Lowe, J. Chem. Soc; 103339, (1934).
[20] J.F. Myers, G.W. Rayner Canham, A.B.P. Lever, Inorg.
Chem; 14, 461, (1975).
[21] J.F. van der Pol, E. Neeleman, J.W. Zwikker, R.J.M. Nolte,
W.
Drenth, Trav. Chim. Pays-Bas; 107, 615, (1988)..
146
[22] P.G. Schouten, J.W. Warman, M.P. de Haas, C.F. van

Nostrum,
G.H. Gelinck, R.J.M. Nolte, M.J. Copyn, J.W. Zwikker, M.K.
Engel, M. Hanack, Y.H. Chang, W.T. Ford, J. Am. Chem. Soc;
116,
6880, (1994).
[23] J. Simon, P. Bassoul, Phthalocyanine based liquid
crystals: towards submicronic devices, in: C.C. Leznoff, A.B.P.
Lever (Editors), Phthalocyanines, Properties and
Applications , vol. 2, VCH Weinheim, Germany, (1993).
[24] D. Guillon, A. Skoulios, C. Piechocki, J. Simon, P. Weber,
Mol.
Cryst. Liq. Cryst; 100, 275, (1983).
[25] C. Piechocki, J. Simon, J.J. Andre, D. Guillon, P. Petit, A.
Skoulios,
P. Weber, Chem. Phys. Lett; 122, 124, (1985).
[26] M.K. Engel, P. Bassoul, L. Bosio, H. Lehmann, M. Hanack,
J.
Simon, Liq. Cryst;15, 709, (1993).
[27] K. Ohta, L. Jacquemin, C. Sirlin, L. Bosio, J. Simon, New J.
Chem;
12, 751, (1988).
[28] G.J. Clarkson, N.B. McKeown, K.E. Treacher, J. Chem.
Soc. Perkin
Trans; 1, 1817, (1995).
147
[29] N. Kobayashi, Curr. Opin. Solid State Mater. Sci; 4, 345,

(1999).
[30] Moser FH, Thomas AL. Properties. In: The
phthalocyanines , vol. 1. Boca Raton, FL, CRC Press, (1983).
[31] Leznoff CC, Lever ABP. Phthalocyanines properties and
applications VCH,Weinheim, (1989).
[32] A. Braun, J. Tcherniac, Ber. Dtsch. Chem. Ges; 40, 2709,
(1907).
[33] H. de Diesbach, E. von der Weid, Helv. Chim. Acta; 10,
886, (1927).
[34] A.G. Dandridge, H.A.E. Drescher, J. Thomas, Dyes British
Patent, 322 (1929)169.
[35] R. P. Linstead, Br. Ass. Adv. Sci. Rep; 465, (1933).
[36] R. P. Linstead, J. Chem. Soc; 1016, (1934).
[37] J. M. Robertson, J. Chem. Soc; 615, (1935).
[38] C.C. Leznoff, A.B.P. Lever, Editors, Phthalocyanines:
Properties and Applications vol. 1-4, VCH Publishers, New
York (1989-1993).
[39] R. Bonnett, Chemical Aspects of Photodynamic
Therapy , Gordon and Breach Science Publishers, Germany,
(2000).
[40] Y. Chen, D. Dini, M. Hanack, M. Fujitsuka, O. Ito, Chem.
Commun; 340, (2004).
[41] H.I. Beltrn, R. Esquivel, A. Sosa-Snchez. Inorg. Chem;
43, 3555, (2004).
[42] E.A. Ough, M.J. Stillman, Inorg. Chem; 33, 573, (1994).
148
[43] I. Chambrier, M.J. Cook , P.T. Wood. Chem. Commun; 56,

2133. (2000).
[44] P. Yiru, H. Fenghua, L. Zhipeng, C, Naisheng, H. Jinling,
Inorg. Chem. Commum; 7, 967, (2004).
[45] C.E, Dent, R.P, Linstead, J. Chem. Soc; 1027, (1934).
[46] N. Kobayashi, A.B.P. Lever, J. Am. Chem. Soc; 109, 7433,
(1987).
[47] A.R. Monahan, J.A. Brado, A.F. DeLuca, J. Phys. Chem;
76, 1994, (1972).
[48] R. D. George, A. W. Snow, J. S. Shirk, W. R. Barger, J.
Porphyr. Phthalocya; 2, 1, (1998).
[49] M. J. Stilman, T. Nyokong, in Phthalocyanines:
Properties and Applications (Editors). C. C. Leznoff, A. B. P.
Lever, VCH, New York, (1989).
[50] A. Ogunsipe, T. Nyokong, J. Photochem. Photobiol. A:
Chem; 173, 211, (2005).
[51] E.S. Emerson, M.A. Conlin, A.E. Rosenoff, K.S. Norland,
H. Rodriguez, D. Chin, G.R. Bird, J. Phys. Chem; 71, 2396,
(1967).
[52] E. Coates, J. Soc. Dyers. Col; 85, 355, (1969).
[53] M. Kasha, Radiat. Res; 20, 55, (1960).
[54] H. Enkelkamp, R.J.M. Nolte, J. Porphyr. Phthalocya; 4,
454, (2000).
[55] S.E. Sheppard, A.L. Gedder,J. Am. Chem. Soc; 66, 1944,
(1995).
149
[56] H. Kobayasbi, Y, Torri, , N, Fakuda, J. Chem. Soc; 81,694,

(1960).
[57] Z.A, Schelly, R.D, Farina, E.A. Eyring, J. Pbys. Chem;
74,617, (1970).
[58] P.D.W. Boyd, T.n. Smith, J. Chem. Soc. (Dalton Trans);
839, (1972).
[59] A.W. Snow, , N.L. Jarvis, J.Am. Chem. Soc; 106,4706,
(1984).
[60] W.L. k. Reynolds, I.I. Kolstad, J.lnorg. Nucl. Chem;38,
1835, (1976).
[61] H. Sigel, P. Waldmeir, B. Prijs, Inorg. Nucl. Chem. Lett; 7,
161, (1971).
[62] A.B.P. Lever, C.C. Leznoff, Phthalocyanines Properties,
and Applications , vols.14, VCH, New York, (19891996).
[63] A, Kalkan, A. Koca, Z.A. Bayr, Polyhedron; 23, 3155-62,
(2004).
[64] C.H. Lee, D.K.P. Ng, Tetrahedron Lett; 43, 4211-13,
(2002).
[65] P. Gregory. Industrial Applications of Phthalocyanines. J
Porphyrins and Phthalocyanines; 4:434, (2000).
[66] H.G. Tanner, ( E.I. du Pont de Numours & Co) U.S. Patent
2, 163, 768, (June 27, 1939).
[67] Ciba Ltd., British Patent 685,582 , (Jan. 27, 1953).
[68] R.E. Colwell, N. Platzer, ( Monsanto Chemical Co.) U.S.
Patent 2,857,341 (Oct. 21, 1958).
150
[69] E.E. Walker, M.P. Shaw, V.W.F. Fisher, ( Brtish Celanese

Ltd.) U.S. Patent 2, 825, 655 (Mar. 4, 1958).
[70] H. Taul, H. Iodest, (Vereinigte Glanzistoff-Fabriken A.G. )
U.S Patent 2,997,450 (Aug. 22, 1961).
[71] A. Sander, Die Chemie; 55, 255, (1942).
[72] R. Gopala , T.P. Z. Sastri, Anal. Chem; 160, 109.
[73] M. Calvin, E.G. Cockbain, Polyani, M. Trans. Faraday Soc;
32, 1443, (1936).
[74] Polyani, M. Trans. Faraday Soc;34, 1191, (1938).
[75] Paquot, C. Bull. Soc. Chim; 8, 695, (1941).
[76] Paquot, C. Campt. Rend; 214, 173, (1942).
[77] Paquot, C. Bull. Soc. Chim; 12, 450, (1945).
[78] Uni, N. Nature; 177, 1177, (1956).
[79] W.M. Brouwer, D.A.M. Traa, W. De, W. Piet, Angew
Makromol.
Chem; 128, 133, (1984).
[80] L.M. Santos, M. Baldwin, Anal. Chem; 58, 848, (1986).
[81] F.H. Moser, A.L. Thomas, "The Phthalocyanines", VoL.l,
CRC Press, Boca Ration, F.L. (1983).
[82] H. Behret, H. Binder, G. Sandstete, G.G. Scherer, J.
ElectroanaI. Chem; 29,117, (1981).
[83] J. Zagel, R.K. Sen, E. Yeager, J. Electroanal. Chem; 83,
207, (1977).
[84] T. Kuwana, M. Fujihira, K. Sunakawa, T. Osa, J.
Electroanal. Chem; 88,299, (1978).
[85] Randin, J.P. Electrochim Acta; 19,83, (1974).
151
[86] J. Zagal, P. Bindra, E. Yeager, J. Electrochem. Soc; 127,

1506, (1980).
[87] N. Kobayashi, Y. Nishiyama, J. Phys. Chem; 89, 1167,
(1985).
[88] T.T. Osaka, K. Naol, T. Hirabayashi, S. Nakamura, Bull.
Chem. Soc; 59, 2717, (1986).
[89] A. Elzing, A. Vander Putten, W. Visscher, E. Barendrecht,
J. Electroanal. Chem; 233, 113, (1987).
[90] J. Blomquist, U. Helgeson, L.C. Mobery, L.Y. Johnson, R.
Larson, J. Electrochem. Acta; 27,1445, (1982).
[91] Toshiba Corp. Jpn. Kokai Tokkyo Koho Jp. Appl. 81/41,
673,24 March 1981, CA. 1985, 102, 754174.
[92] M. Savy, P. Anddro, C. Bernard, J. Electrochem Acta; 19,
403, (1974).
[93] G.A. Alfemov, Sevast'yenov. J. Electrochimiya;, 11,827,
(1975).
[94] M. Meshitsuka, K. Tamaru, J. Chem. Soc. Faraday Trans;
73, 236, (1977).
[95] C. Linkous, T. Klofta, N.R. Annstrong, J. Electrochem. Soc;
130, 1050, (1983).
[96] M.K. Halbert, RP. Baldwin, Anal.Chem; 57,591, (1985).
[97] K.M. Korfhage, K. Ravicharndran, R.P. Baldwin, Anal.
Chem; 57, 1514, (1984).
[98] H. Tachikawa, L.R. Faulkner, J. Am. Chem. Soc;
100,4379, (1978).
152
[99] F. Fu Ren , L.R. Faulkner, J. Am. Chem. Soc; 101,4779,

(1979).
[100] S. Meshitsuka, K. Tamar, J. Chem. Soc Faraday Trans;
1, 73, 23, (1977).
[101] H. Riel, W. Brutting, T. Beierlein, E. Haskal, P. Muller, W.
Rie, SyntheticMet. 303, 11112 (2000).
[102] K. Shinbo, E. Sakai, F. Kaneko, K. Kato, T. Kawakami, T.
Tadokoro, S. Ohta, R.C. Advincula, IEICE Trans. Electron. E85C 1233, (2002).
[103] K. Shinbo, M. Minagawa, H. Takasaka, K. Kato, F.
Kaneko,
T. Kawakami, Colloids Surf. A 905, 198200, (2002).
[104] S, Grammatica, Mort, J. Appl. Physics Lett; 38,445,
(1981).
[105] A. Kakuta, , Y. Mori, S. Takano, M. Sawada, I. Shibuya, J.
Imag, Technol., 8, 7, (1985).
[106] A.K. Ghosh, D.L. Morel, T. Feng, R.F. Shaw, C.A. Rowe, J.
Appl. Phys; 45, 230, (1974).
[107] M. Shimura. A. Toyoda, J. Appl. Phys; 23,1462, (1984).
[108] R.O. Loutfy, L.F. Mclntyne. Energy Mater; 6, 467,
(1982).
[109] K. Petritsch, J.J. Dittmer, E.A. Marseglia, R.H. Friend, A.
Lux,
G.G. Rozenberg, S.C. Moratti, A.B. Holmes, Sol. Energy Mater.
Sol. Cells; 61, 63, (2000).
153
[110] A. Sobezynski, J.M. White. J. Mol. Catal; 29, 379,

(1985).
[111] R.S. Magloiozzo, A.I. Krasana, Photochem. Photobiol;
38, 15, (1983).
[112] P.N. Moskalev, N.I. Alimova, J. Inorg. Chem; 41, 251,
(1967).
[113] P.N. Moskalev, I.S. Kirin. J. Phys. Chem; 46, 1019,
(1972).
[114] J.M. Green, L.R. Faulkner, J. Am. Chem. Soc; 105, 2950,
(1983).
[115] C.L. Lin, C.C. Lee, K.C. Ho, J. Electroanal. Chem; 81,
524, (2002).
[116] Toshiba Corp. Jpn. Kokai Tokkyo, Koho lP. 57, 157.468
(82, 157,468) 1982 CA. 1983, 75417.
[117] Doddapaneni. N. Eur. Pat. Appl. E.P 57, 986. 1982. CA
1983, 19510m.
[118] J.l. Miasik, A. Hooper. B.C. Tofield, J. Chem. Soc. Faraday
Trans; 82, 1117, (1986).
[119] Sawa Seikosha Co., Ltd. Jpn. Kokai Tokkyo Koho JP 57,
108,652, 1982. CA 1983, 46165j.
[120] M.I. Newton, T.K.H. Starke, M.R. Willis, G. McHale,
Sensors
Actuators B: Chem; 67, 307, (2000).
[121] Royo Ink Mfg. Ltd. Jpn. Kokai, Tokkyo Koho JP 59, 116.
754. 1982. CA 1985, 123055d.
[122] C.E. Dent, R.P. Linstead, J. Chem. Soc. 1027, (1934).
154
[123] E.A. Lawton, McRitchie, Research on Thermostable

Molecules and Polymers, WADC Technical Report 57-642.
ASTIA Document no.AD 142199, 1957.
[124] Lonsdale K. Magnetic anisotropy and electronic
structure of aromatic molecules. Proc R Soc, London Ser A;
159, 14961, (1937).
[125] G.F.D. Alelio, U.S. Patent 3,996,196, December 7, 1976.
[126] J.R. Griffith, J.G.O. Rear, U.S. Patent 3,993,631,
November 23, 1976.
[127] J.R. Griffith, J.G.O. Rear, U.S. Patent 4,056,560,
November 1, 1977.
[128] K.J. Wynne, J.B. Davision, U.S. Patent 4,132,842,
January 2, 1979.
[129] T.M. Keller, J.R. Griffith, U.S. Patent 4,234,712,
November 18, 1980.
[130] F.H. Moser, A.L. Thomas, The Phthalocyanine , vols.
1 and 2, CRC
Press, Boca Raton, FL, (1983).
[131] B.N. Achar, G.M. Fohlen, J.A. Parker, U.S. Patent
4,450,268, May
22, 1984.
[132] M. Hanack, in: J. Ladik, J.J. Andre (Editors.), Quantum
Chemistry of Polymers-Solid State Aspects , p. 112, (1984).
[133] J.W.P. Lin, L.P. Dudek, J. Polym. Sci. Polym. Chem. Ed;
23, 1579, (1985).
155
[134] J.W.P. Lin, L.P. Dudek, J. Polym. Sci. Polym. Chem. Ed.
23
1589, (1985).
4,499,260,
Febuary 12, 1985.
4,522,755, June
11, 1985.
4,537,834, August
27, 1985.
4,649,189, March
10, 1987.
[139] T.M. Keller, R.F. Gatz, Polym. Commun; 28, 334, (1987).
[140] T. Pascal, J. Malinge, B. Sillion, P. Claudy, J.M. Letoffe, J.
Polym.
Sci., Part A: Polym. Chem; 26, 865, (1988).
[141] A.J. Heeger, S. Kivelson, J.R. Schrieffer, W.P. Su, Rev.
Mod. Phys;
60, 781, (1988).
[142] S. Venkatachalam, V.N. Krishnamurthy, Ind. J. Chem;
33 (A)
506, (1994).
156
[143] S. Venkatachalam, in: H.S. Nalwa (Editor.), Handbook

of Organic Conductive Molecules and Polymers , vol. 2, John
Wiley and Sons, West
Sussex, , pp. 741771, (1997).
[144] M. Hanack, L.R. Subramanian, in: H.S. Nalwa (Editor),
Handbook
of Organic Conductive Molecules and Polymers , vol. 1,
Wiley, New York, p. 687, (1997).
[145] S. Venkatachalam, in: H.S. Nalwa (Editor), Handbook
of Organic Conductive Molecules and Polymers , vol. II,
Wiley, New York, p. 741, (1997).
[146] N.B. Mckeown, J. Mater. Chem; 10, 1979, (2000).
[147] D.D. Eley, Nature; 162, 819, (1948).
[148] A.T. Vartanyan, Zhur. Fiz. Khim; 22, 769, (1948).
[149] C.J. Schramm, R.P. Scaringe, D.R. Stijakovic, B.M.
Hoffman,
J.M. Ibers, T.J. Marks, J. Am. Chem. Soc; 102, 6702, (1980).
[150] T.J. Mark, Angew. Chem., Int. Ed. Engl; 29, 857, (1990).
[151] A. Rosa, E.J. Baerends, Inorg. Chem; 32, 5637, (1993).
[152] L. Kreja, W. Czerwinski, J. Mater. Sci. Lett; 11, 538,
(1995).
[153] C. Park, Y.W. Park, Synth. Met; 71, 2295, (1995).
[154] A.M. Paoletti, G. Pennesi, G. Rossi, C. Ercolani, Inorg.
Chem;
34, 4780, (1995).
157
[155] R. Singerski, J. Kalinowski, I. Davoli, S. Stizza, Phys.

Status
Solidi (A); 125, 597, (1991).
[156] J. Keshavayya, Ph.D. Thesis, University of Mysore,
(1988).
[157] J.M. Bhandari, Ph.D. Thesis, University of Mysore,
(1992).
[158] B.N. Achar, P.K. Jayashree, Synth. Met; 104, 101,
(1999).
[159] B.N. Achar, P.K. Jayashree, Can. J. Chem; 77, 1690,
(1999).
[160] B.N. Achar, P.K. Jayashree, Synth. Met. 114 (2000) 219.
[161] B.N. Achar, P.K. Jayashree, Synth. React. Inorg. Met.
Org.
Chem; 30, 719, (2000).
[162] R. W. Gerdes, D. orhle, W. Spiller, G. Schneider, G.
Schnurpfeil, G. Schulz-Ekloff, J. Photochem. & Photobio. A:
Chem; 111, 65-74, (1997).
[163] A.W. Snow, J.S. Shirk, R.G.S. Pong, J. Porphyrins &
Phthalocyanines; 4, 518-24, (2000).
[164] S.G. Liu, Y.Q Liu, Y. Xu, D.B. Zhu, A.C. Yu, X.S. Zhao.
Langmuir; 14, 690-95, (1998).
[165] B. Cosimelli, G. Roncucci, D. Dei, L. Fantetti, F. Ferroni,
M. Ricci, D. Spinelli, Tetrahedron; 59, 10025-10030, (2003).
[166] A. G. Hirth, N.Trombach, J. Porphyrins &
Phthalocyanines; 3, 230-37, (1999).
158
[167] G. Torre, C. G. Claessens, T. Torres, Chem. Commun;

2000, (2007)
[168] (a) I. J. MacDonald, T. J. Dougherty, J. Porphyrins &
Phthalocyanines; 5, 105, (2001);
(b) D. E. J. G. J. Dolmans, D. Fukumura, R. K. Jain, Nat. Rev.
Cancer; 3, 380, (2003);
(c) M. R. Detty, S. L. Gibson, S. J. Wagner, J. Med. Chem; 47,
3897, (2004).
[169] W.X. Chen, W.Y. Lu, Y.Y. Yao, M.H. Xu, Environ. Sci.
Technol; 41, 6240, (2007).
[170] (a) H. Ali, J. E. Van Lier, Chem. Rev; 99, 2379, (1999);
(b) T. Nyokong, Coord. Chem. Rev; 251, 1707, (2007).
[171] M. Hanack, M. Lang, Chemtracts Org. Chem; 8, 131,
(1995).
[172] D. K. P. Ng, C.R. Chim;, 6, 903, (2003).
[173] B.N. Achar, G.M. Fohlen, J.A. Parker, J. Polym. Sci. Part
A; 25,
443, (1987).
[174] N.B. Mckeown, J. Mater. Chem; 10, 1979, (2000).
[175] B.N. Achar, K.S. Lokesh, J. Organomet. Chem; 689,
2601, (2004).
[176] (a) B.N. Achar, P.K. Jayasree, Can. J. Chem; 77, 1690,
(1999).
(b) B.N. Achar, K.S. Lokesh, J. Organomet. Chem; 689, 3357,
(2004).
159
[177] (a) P.A. Barrett, C.E. Dent, R.P. Linstead, J. Chem. Soc;
1719, (1936);
(b) I.M. Heilborn, F. Irving, R.P. Linstead, ( Imperial Chemical
Industries Ltd.,), US Patent 2,116,602 (May 10, 1939); British
Patent
410,814 (May 16,1934);
(c) R.P. Linstead, A.R. Lowe, J. Chem. Soc; 1022, (1934).
[178] C.G. Claessens, W.J. Blau, M. Cook, M. Hanack, Nolte
RJM, Torres T, et al. Phthalocyanines and Phthalocyanine
Analogues: the quest for applicable optical properties.
Monatshefte fr Chemie;132, 3-11, (2001).
[179] K. Petrisch, J.J. Dittmer, E.A. Marseglia, R.H Friend, A.
Lux, G.G Rozenberg, et al. Dye-based donor/acceptor solar
cells. Solar Energy Materials & Solar Cells; 61, 63-72, (2000).
[180] T.H. Wei, T.H. Huang. A study of photophysics using the
Z-scan technique: lifetime determination for high-lying
excited states. Optical and Quantum Electronics; 28,1495,
(1996).
[181] D.J. Mascaro, C.D. Dimitrakopoulos. Organic thin-film
transistors: a review of recent advances. IBM Journal of
Research and Development; 45(1), 11-27, (2001).
[182] M. Pfeiffer, K. Leo, X. Zhou, J.S. Huang, M. Hofmann, A.
Werner, et al. Doped organic semiconductors: physics and
application in light emitting diodes. Electron Beam
Lithography;4, 89-103, (2003).
160
[183] T.S. Shafai, R.D. Gould. Transport properties in lead

phthalocyanine thin films for use in FET structures.
International Journal of Electronics and Communications; 69,
3-7, (1990).
[184] T.S. Shafai, R.D. Gould. Observations of Schottky and
Poole-Frenkel emission in lead phthalocyanine thin films
using aluminum injecting electrodes. International Journal of
Electronics and Communications;73, 307-12, (1992).
[185] E.I. Haskal, A. Curioni, P.F. Seidler, W. Andreoni.
Lithium-aluminum contacts for organic light-emitting
devices. Applied Physics Letters; 71, 1151-3, (1997).
[186] M. Biler, I. Zhivkov, J. Rakusan, M. Karskov, S.
Pochekailov, G. Wang, et al. Soluble phthalocyanines - new
materials for optoelectronics. Journal of Optoelectronics and
Advanced Materials; 7,1365-70, (2005).
[187] C.J. Brabec, F. Padinger, J.C. Hummelean, R.A.J.
Janssen, NS. Sariciftci. Realization of large area flexible
fullerene - conjugated polymer photocells: a route to plastic
solar cells. Synthetic Metals;102:861-4, (1999).
[188] M. Al-Ibrahim, H.K. Roth, U. Zhokhavets, G. Gobsch, S.
Sensfus. Flexible large area polymer solar cells based on
poly(3-hexylthiophene)/fullerene. Solar Energy Materials &
Solar Cells; 85, 13-20, (2005).
[189] P. Peumans, A. Yakimov, S.R. Forrest. Small molecular
weight organic thin-film photodetectors and solar cells.
Journal of Applied Physics; 93,3693, (2003).
161
[190] D. Natali, M. Sampietro, M. Arca, C. Denotti, F.A.

Devillanova. Wavelength-selective organic photodetectors
for near-infrared applications based on novel neutral
dithiolenes. Synthetic Metals;137, 1489-90, (2003).
[191] M.C. Scharber, D. Muhlbacher, M. Koppe, P. Denk, C.
Waldauf, A.J. Heeger, et al. Design rules for donors in bulkheterojunction solar cell-towards 10% energy-conversion
efficiency. Advanced Materials;18, 789, (2006).
[192] M. D. Kwena . Synthesis and Photophysical
Properties of Antimony and Lead Phthalocyanine . Rhodes
University; 44-46, (2009).
[193] W.M. Sharman, C.M. Allen, J.E. van Lier,
Photodynamic thera- peutics: Basic Principles and Clinical
Applications , Drug Discov Today; 4 507517, (1999).
[194] D. Phillips, V. Eigenbrot, T.C. Oldham, Spectroscopic
Studies of Drugs used in Photodynamic Therapy, in: R.J.H.
Clark, R.E. Hester (Editors.), Biomedical Applications of
Spectroscopy; Wiley, New York, 1996.
[195] S. Wan, J.A. Parrish, R.R. Anderson, M. Madden,
Transmittance of
nonionizing radiation in human tissues, Photochem.
Photobiol; 34, 679681, (1981).
[196] D. Wohrle, A. Hirth, T. Bogdahn-Rai, G. Schnurpfeil, M.
Shopova,
162
Photodynamic Therapy of Cancer: second and third

generations of photosensitizers, Russ. Chem. Bull; 47, 807
816, (1998).
[197] R. Bonnett, Photosensitizers of porphyrin and
phthalocyanines series
for photodynamic therapy, Chem. Soc. Rev; 24, 1933,
(1995).
[198] I. Rosenthal. Phthalocyanines as photodynamic
sensitizers. Journal
of Photochemistry and Photobiology; 53, 859 -70, (1991).
[199] J. Griffiths, J. Schofield, M. Wainwright, S.B. Brown.
Some observations on the synthesis of polysubstituted zinc
phthalocyanine sensitisers for photodynamic therapy. Dyes
and Pigments;33, 65-78, (1997).
[200] A. Visona, A. Angelini, S. Gobbo, A. Bonanome, G.
Thiene, Pagnan A, et al. Local photodynamic therapy with
Zn(II)-phthalocyanine in an experimental model of intimal
hyperplasia. Journal of Photochemistry and Photobiology B:
Biology; 57, 94-101, (2000).
[201] J.H. Weber, D.H. Busch. Complexes derived from strong
field ligands. XIX. Magnetic properties of transition metal
derivatives of 4,4,4,4-tetrasulfophthalocyanine. Inorganic
Chemistry; 4, 469-71, (1965).
[202] B.A. Bench, A. Beveridge, W.M. Sharman, G.J. Diebold,
J.E. van Lier, S.M. Gorun. Angewandte Chemie International
Edition; 41, 747-50, (2002).
163
[203] J. Usuda, S.M. Chiu, E.S. Murphy, M. Lam, A.L.

Nieminen, N.L. Oleinick. Domain-dependent photodamage to
Bcl-2, a membrane anchorage region is needed to form the
target of phthalocyanine photosensitization. Journal of
Biological Chemistry; 278, 2021-9, (2003).
[204] I. Scalise, E.N. Durantini. Synthesis, properties, and
photodynamic inactivation of Escherichia coli using a
cationic and a noncharged Zn(II) pyridyloxyphthalocyanine
derivatives. Bioorganic Medicinal Chemistry; 13, 3037-45,
(2005).
[205] B. Henderson, T. Dougherty, photochem. Photobiol; 55,
145, (1992).
[206] W. M. Sharman, J.E. van Lier, In the Porphyrin
Handbook , K.M. Kadish, K. M. Smith, R; Guilard, Academic
press, San Diego, Vol. 15, (2003).
[207] R. S. Drago, Physical Methods in Chemistry ,
Saunders, Philadelphia; p. 411, (1977).
[208] P. Atkins et al, Shriver and Atkins Inorganic Chemistry
, 4th ed, W.H. Freeman, New York, (2006).
[209] J. Mack, M. J. Stillman, In The Porphyrin Handbook ,
K. M. Kadish, K.M. Smith, R. Guilard, Academic Press, San
Diego; Vol. 16, 46, (2003).
[210] E. A. V. Ebsworth, D. W. H. Rankin, S. Cradock,
Structural Methods in Inorganic Chemistry ; Blackwell
Scientific, Oxford, (1987).
164
[211] K. Nakamoto, Infrared and Raman Spectra of

Inorganic and Coordination Compounds , 4th edition, Wiley,
New York, (1986).
[212] R. C. Mackenzie, Thermochim. Acta; 28, 1, (1979.)
[213] S. P. J. Higson, Analytical Chemistry , Oxford
University Press, Inc, New York, (2004).
[214] J. Basset, R. C. Denney, G. H. Jeffery. J. Mendham,
Text Book of Quantitative Inorganic Analysis , 4th edition,
Longman Group Limited, England, (1978).
[215] D. L. Pavia, G. M. Lampman, G. S. Kriz, Introduction to
Spectroscopy , 3d edition, Thomson Learning. Inc,
Washington, (2001).
[216] R. M. Silverstein, F. X. Webster, D. J. Kiemle,
Spectrometric Identification of Organic Compounds , 7th
edition, John Wiley & sons. Inc, New York, (2005).
[217] k. Klemm, W.W. Land Klem, J. Prakt. Chem.; 43, 82,
(1935).
[218] T. J. Marks, Science; 227, 881, (1985).
[219] M. Hanack, M. Lang, Adv. Mater; 6, 819, (1994).
[220] J.V. Bakboord, M.J. Cook, E. Hamuryudan, J. Porphyr.
Phthalocya; 4 510, (2000).
[221] W. Eberhardt, M. Hanack, Synthesis; 95, (1997).
[222] A.B.P. Lever, Adv. Org. Chem. Radiochem; 7, 27,
(1965).
[223] C.G. Barraclough, R.L. Martin, S. Mitra, R.C. Sherwood,
J. Chem. Phys; 53, 1643, (1970).
165
[224] M.S. Liao, S. Scheiner, J. Chem. Phys; 114, 9780,

(2001).
[225] M.S. Liao, S. Scheiner, J. Comp. Chem; 23, 1391,
(2002).
[226] M.S. Liao, J.D. Watts, M.J. Huang, J. Phys. Chem. A; 109,
(2005).
[227] M. Sumimoto, Y. Kawashima, K. Hori, H. Fujimoto,
Spectrochim. Acta A; 71, 286, (2008).
[228] N. Marom, O. Hod, G.E. Scuseria, L. Kronik, J. Chem.
Phys; 128 164107, (2008).
[229] N. Marom, L. Kronik, Appl. Phys. A; 95, 165, (2009).
[230] N. Marom, L. Kronik, Appl. Phys. A; 95, 159, (2009).
[231] F. A. Cotton. G. Wilkinson. Advanced Inorganic
Chemistry 4th
edition, John Wiely and sons, Inc, New York, (1980).
[232] A.W. Bauer, W.M. Kirby, C. Sherris, M. Turack, Antibiotic
susceptibility testing by a standardized single disk method,
American Journal of Clinical Pathology; 45, 493-496, (1966).
[233] National Committee for Clinical Laboratory Standards.
(1993) Performance VOL.41,(1997) antimicrobial
susceptibility of Flavobacteria.
[234] T. Mosmann, Rapid colorimetric assay for cellular
growth and survival: application to proliferation and
cytotoxicity assays. J. Immunol. Methods; 65, 55-63, (1983).
166
[235] p. Vijayan, C. Raghu, S.A. Dhanaraj, B. Suresh, Antiviral

activity of medicinal plants of Nilgiris. Indian J. Med. Res;
120, 24-29, (2004).
[236] A.M. Schaffer, M. Gouterman, E.R. Davidson, Theor. Chim. Acta; 30
9, (1973) .
[237] A.B.P. Lever, Adv. Inorg. Chem. Radichem; 7, 27, (1965).
[238] D.W. Boyd, T.D. Smith, J. Chem. Soc., Dalton Trans; 839, (1972).
[239] L.M. Mink, M.L. Neitzel, L.M. Bellomy, R.E. Falvo, R.K. Boggess,
B.T. Trainum, P. Yeaman, Polyhedron; 16, 2809, (1997).
[240] I. Edwards, M. Gouterman, J. Mol. Spectrosc; 33, 292, (1970).
167

Research of Phthalocyanines

Загружено:

Сведения о документе

Исходное описание:

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Research of Phthalocyanines

Загружено:

Авторское право:

Доступные форматы

1.0.

not only capable of undergoing classical displacement reactions, but they

Fig.1.1: Phthalocyanine structure

Scheme 1.1: First preparationof a metal-free phthalocyanine

1.1.2. Structure of phthalocyanine

Fig.1.2: Molecular structures of tetrapyrole macrocycles

Fig.1.3: Numbering scheme for phthalocyanine

The coordination of the Phthalocyanine ligand with metal and metalloid

Scheme 1.2: Synthetic routes of MPcs from starting

The first step in the purification of phthalocyanine involves washing with

The H-aggregate 51 is a cofacial arrangement, which readily allows

Fig. 1.4: Electronic transitions in phthalocyanines aggregates

Aggregation behaviour of Phthalocyanines is generally investigated by

respectively. The concentration equilibrium constant for dimer formation,

ubiquitous azo colorants in terms of commercial importance. The major

tetrasulphophthalocyanine is attached to poly (vinylamine) it can catalyses

The reduction of dioxygen at iron tetrasulfonatophthalocyanine (FeTSP)

are modified by the incorporation of cobalt phthalocyanine is able to oxidize

Cobalt tetrasulfophthalocyanine covalently bound on the surface of titanium

Electrochromism of phthalocyanines are very interesting for developing new

nature, semiconductivity, photoconductivity and catalytic activities have

. The effect of substituents and the peripheral phenyl groups of the

phthalocyanine structure seems to yield much information about the nature

great attention because of their versatile applications 16,17,167. One of their

The discovery of semiconducting properties of metal

in the electrical properties of phthalocyanines which has

Electrical conductivity of metal phthalocyanines is very

Phthalocyanines are an important class of organic materials

Phthalocyanine chemistry is undergoing a renaissance

the flexibility in tailoring the electrical and optical properties,

, optical recording, optical memories, information

, hole-burning memories, light-limiters, lasers,

non-linear optical elements, etc.

. The photoactive semi-

conducting properties of phthalocyanine monomers and

. In organic photovoltaic devices, dissociation of photo-

generated excitations occurs leading to photocurrent in the

Since the discovery and invention of intense light sources

of laser weapons. Thus eye and sensor protection systems

Fig.1.5: Laser light on aircraft

of laser threats and as a result they do not protect the eyes.

For clinical photodynamic therapy (PDT), the

However, as these compounds absorb light of relatively short

compounds with absorption bands of longer wavelength are

, and intimal hyperplasia201.

Phthalocyanines have also been used in photo-inactivation of

. PDT dyes are recognized as efficient sensitizers

of singlet oxygen and the involvement of singlet oxygen in

Scheme 1.3: Potential applications of phthalocyanines

1.1.7. Geometry of phthalocyanine

geometry of the macrocycle, forming C4v symmetry. This symmetry is a

Fig.1.6: Geometry of phthalocyanines

Fig.1.7: Constitutional isomers of non-peripherally substituted MPcs.

1.1.8. UV-Visible Spectroscopy

nature of the bonding) in transition metal complexes. Most

1.1.8.1. Electronic structure and spectroscopy of

Fig.1.8: Molecular structure of a MPc showing the

1.1.9. Infrared Spectroscopy

C single bond are similar for most molecules) so that

1.1.10. Thermogravimetric Analysis (TGA)

. The resulting mass-temperature profiles are known as

thermograms. The balance pan and sample are enclosed

and uniform temperatures may be achieved and (ii) prevent