Redox chemistry, spectroelectrochemistry and catalytic activity of novel synthesized phthalocyanines bearing four schiff bases on the periphery

Article abstract of DOI:10.1016/j.jorganchem.2016.08.013

The synthesis and characterization of novel metallophthalocyanines (M?=?Zn, Co) carrying four schiff base on four peripheral positions were realized. These complexes have been characterized by a combination of FT-IR, 1H NMR, HRMS and UV–Vis spectroscopy t

Full text of DOI:10.1016/j.jorganchem.2016.08.013

Accepted Manuscript
Redox chemistry, spectroelectrochemistry and catalytic activity of novel synthesized
phthalocyanines bearing four schiff bases on the periphery
Hüseyin Karaca
PII:
S0022-328X(16)30347-3
10.1016/j.jorganchem.2016.08.013
JOM 19592
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 25 May 2016
Revised Date: 12 August 2016
Accepted Date: 16 August 2016
Please cite this article as: H. Karaca, Redox chemistry, spectroelectrochemistry and catalytic activity of
novel synthesized phthalocyanines bearing four schiff bases on the periphery, Journal of Organometallic
Chemistry (2016), doi: 10.1016/j.jorganchem.2016.08.013.
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Redox Chemistry, Spectroelectrochemistry and Catalytic Activity of Novel Synthesized
Phthalocyanines Bearing Four Schiff Bases on The Periphery
Hüseyin Karaca
Department of Chemistry, Sakarya University, 54187 Sakarya, Turkey
Tel.:+90 264 295 60 49; fax: +90 264 295 59 50.
E-mail address: karaca@sakarya.edu.tr
Abstract
The synthesis and characterization of novel metallophthalocyanines (M = Zn, Co) carrying
four schiff base on four peripheral positions were realized. These complexes have been
characterized by a combination of FT-IR, 1H-NMR, HRMS and UV–Vis spectroscopy
techniques. Electronic absorption spectra showed that both Pcs are nonaggregable molecules
and also well solubles common organic solvents such as dichloromethane, chloroform, THF,
DMSO and DMF. Cyclic voltammograms give two reduction reaction for Pc-6 and one
reduction reaction for Pc-7. The spectroelectrochemical investigation shows the ring based
reduction potential for MPc’s. Pc-7 cobalt(II)phthalocyanine was investigated as catalyst in
the catalytic oxidation of 2-mercaptoethanol. Turnover number, initial reaction rate and the
oxygen consumption was found in the catalytic oxidation of 2-mercaptoethanol as 18.6, 0.34,
2.75 recpectively.
Keywords: schiff base, phthalocyanine, redox, catalysis, UV-Visible

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1. Introduction
Phthalocyanines (Pcs) are very interesting molecules because of their structural flexibility
[1]. Over the years, metallophthalocyanines have been subjected to several investigations.
Because peripherally functionalization of phthalocyanines uncovers the unique properties. So
these properties have being applied on the areas such as dyes and catalysts [2], organic
photovoltaic devices [3-6], photodynamic therapy [7-12], electrochemical applications [13-
15], low-dimensional conductors [16,18], chemical sensors [19-23], optical data storage [24],
Langmuir-Blodgett films [25,26] and liquid crystals [27-29]. As two-dimensional planar
aromatic molecules phthalocyanines are having 18 π-electron system and giving hope for new
properties arises from their conjugated macrocycle units. The synthesized molecule must be
soluble either in organic solvents or water in orderto obtain and study new properties by
derivatization [30]. This issue could be coped with two ways. One, by substituting the bulky
groups in peripheral positions or non-peripheral positions. Two, changing the central metal
atom that can bind solvents [2].
Schiff base chemistry is a versatile tool in organic synthesis and has impressive various
achievements. It has played an important role in the development of coordination chemistry.
Most of the articles are about to form complexes with transition metals [31]. Schiff bases are
important for various fields of chemistry and biochemistry because of having the biological
activity. They are subjected to medicine, antifungal, antibacterial and anticancer researches
[32,33]. Furthermore many studies of these compounds have been published on the
complexation with metals for the construction of new molecular materials since they have
attractive biological, catalytical and physicochemical properties [34-39]. In addition to all
those mentioned above schiff bases have photochromic properties [40-43]. Combining the
schiff bases with pthalocyanines will reveal interesting new features. Schiff base substitutes
phthalocyanines could make complexes with many metals, have photoluminescence
properties and have chance to use as a catalyst. In this study we have investigated redox
chemistry, spectroelectrochemistry and the catalytic activity of metallophthalocyanines
combined with a schiff base. The oxidation of 2-mercaptoethanol was inestigated for
Co(II)phthalocyanine as catalytic activity.
The newly designed MPcs having imine moiety on their peripheral positions were
13
characterized by 1H-NMR, C-NMR, IR, MALDI-TOF, and UV/Vis spectra. In this study, I
report the preparation and characterization of new imine substituted phthalocyanines and their
redox chemistry, spectroelectrochemistry and catalytic activity in oxidation of 2-
mercaptoethanol.
2. Experimental
2.1. General
o
All glassware was heated at 150 C for 1h and then was cooled under inert atmosphere of
nitrogen then was used in the experiments of this work. The reaction solvents were distilled
from the indicated drying agents: DMAE (CaH2), DMF (CaH2). All fine chemicals purchased

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from commercial suppliers and used without further purification. Melting points of the
synthesized molecules were obtained on a Barnstead Electrotermal 9200 model melting point
apparatus. Thick-walled glass column was used for flash column chromatography with flash
grade silica (Merck Silica Gel 60). The precoated silica gel plate (Merck Silica Gel PF-254)
was used to achieve the reaction monitoring through thin layer chromatography (TLC).UV-
light and polymolibdenum phosphoric acid in ethanol was used to visualize the spots on the
TLC plate. All extracts were dried over anhydrous magnesium sulfate and solvents was
evaporated under vacuum by using a rotary evaporator.
2.2. Spectroscopy
1
The NMR spectra, H NMR and 13C NMR, were taken in CDCl3 and DMSO-d6 on a
VARIAN Infinity Plus 300 MHz NMR spectrometer. Chemical shifts were expressed in ppm
1
13
relative to CDCl3 (δ7.26 and 77.0 for H and C NMR, respectively) and DMSO-d6 as the
internal standarts. For recording of Infrared spectra a Perkin Elmer Spectrum Two FT-IR
spectrometer was used. HRMS and MALDI-TOF spectra were taken on Bruker Daltonics
flexAnalysis. UV-visible spectroscopy was measured on a Shimadzu UV 2600 model
Spectrophotometer.
2.3. Catalytic oxidation of 2-mercaptoethanol
Catalytic oxidation of 2-mercaptoethanol was carried out by CyberScan DO 300 dissolved
oxygen meter in the closed system. 0.148 ꢀmoL Co(II)phthalocyanine (Co(II)Pc) (Pc-7) was
dissolved in 50 mL THF. Reaction vessel was bubbled with air in oder to obtain oxygen
saturation in the solution. Then 14.7 ꢀL (2.07 mmol) 2-mercaptoethanol was added. The
molar ratio 2-mercaptoethanol as substrate to Co(II)phthalocyanine as catalyst was 14000:1
and this was a good ratio for catalytitc studies. After adding the 2-mercaptoethanol 1 mL of
0.25 wt% aqueous sodium hydroxide solution was added to the reaction vessel and system
was closed. The measurement of the residual oxygen in the reaction mixture was started at the
same time. The oxygen level was measured then time dependent oxygen consumption was
calculated. The catalytic activity of Co(II)phthalocyanine Pc-7 is characterized by turnover
number TON (conversion mol oxygen per mol phthalocyanine), initial reaction rate (ꢀmol
oxygen consumption per second) and the oxygen consumption (ꢀmol/min) [44-46].
2.4. Synthesis
2.4.1. (E)-4-((phenylimino)methyl)phenol, 3

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1 g (8.19 mmol) of 4-hydroxybenzaldehyde (1) and 763 mg (8.18 mmol) of aniline (2)were
mixed in the methanol (MeOH) in a round-bottomed flask. The reaction mixture was stirred
under nitrogen atmosphere at 60oC for 24 h. The reaction mixture was refluxed under vacuum
and washed with a little methanol. Recrystallized in methanol and columned by hexane : ethyl
acetate. Bright yellow solid (1.196 g, 74.1% chemical yield). Melting point: between 191-197
oC. Soluble in common organic solvents such as dichloromethane, chloroform, ethyl acetate,
hexane, ACN. FT-IR (ATR System, cm-1): 3046, 3030, 3003, 2864, 2792, 1829, 1611,1601,
1573, 1514, 1484, 1477, 1442, 1402, 1386, 1316, 1308, 1283, 1264, 1240, 1189, 1163, 1110,
1078, 1022, 1000, 977, 967, 934, 879, 840, 816, 792, 722, 621. 1H NMR (300 MHz, DMSO-
d6) δ8.18 (s, 1H), 7.63-7.56 (m, 2H), 7.27-7.16 m, 2H), 7.06-6.93 (m 3H), 6.81-6.71 (m, 2H),
6.59-6.48 (m, 1H).13C NMR (75 MHz, DMSO-d6) δ 163.7, 161.0, 160.2, 156.8, 132.3, 130.9,
129.3, 129.2, 120.9, 118.7, 116.1, 116.0, 115.5. HRMS: m/z [M] calcd.197.08For C13H11NO :
found [M+H]+198.1.
2.4.2.(E)-4-(4-((phenylimino)methyl)phenoxy)phthalonitrile, 5
377 mg 3 (1.91 mmol) and 331 mg 4-nitrophthalonitril (1.91 mmol) were dissolved in 10 mL
of DMSO in a round-bottom flask and stirred under the nitrogen atmosphere for 30 minutes.
Potassium carbonate (301 mg, 2.17 mmol) was added then continued stirring for 24 h.The
reaction was monitored by TLC.The mixture was poured into 40 mL cold water. The white
solid was obtained and filtered through a sintered funnel then dried over MgSO4 in
chloroform. The obtained product was columned by hexane : ethyl acetate. The white solid
o
(0.367 g, 59.3% chemical yield). Melting point: 177,178 C. FT-IR (ATR System, cm-1):
3084, 3051, 3030, 2890, 2839, 2229, 1756, 1690, 1626, 1605, 1584, 1498, 1446, 1416, 1405,
1366, 1310, 1277, 1247, 1204, 1188, 1166, 1158, 1148, 1101, 1084, 1071, 1036, 1012, 1000,
988, 979, 955, 948, 910, 878, 851, 828, 804, 760, 743, 726, 716, 697, 648, 634, 614. 1H NMR
(300 MHz, CDCl3) δ 8.66 (s, 1H), 8.14 (dd, J=9 Hz, J=3 Hz, 1H), 8.04 (dd, J=9 Hz, J=3 Hz,
2H), 7.90 (t, J=3 Hz, 1H), 7.51 (dt, J=9 Hz, J=3 Hz, 1H), 7.46-7.38 (m, 2H), 7.32 (dd, J=9
Hz, J=3 Hz, 2H), 7.28-7.23 (m, 3H).13C NMR (75 MHz, DMSO-d6) δ160.9, 160.2, 157.2,
152.0, 137.1, 134.0, 131.7 (overlapped 2C signals), 129.9 (overlapped 3C signals), 126.7,
124.2, 123.6, 121.7 (overlapped 3C signals), 120.9, 117.5, 116.6, 109.7.HRMS: m/z [M]
calcd. 323.11 For C21H13N3O; found [M+H]+ 324.1.
2.4.3. Synthesis of Zinc phthalocyanine, Pc-6
5 (331 mg, 1.02 mmol) was dissolved in the 15 mL mixture of DMEA/DMF (1:2). Zinc
acetate dihydrate (56.2 mg, 0.26 mmol) was added to this stirring mixture then refluxed at 160
oC under the nitrogen atmosphere for 24 h. Reaction was finished after TLC controlling. Then
the reaction mixture was poured into the mixture of methanol water (1:1) to stop the reaction.
Obtained dark green solid was dried under vacuum and columned by hexane : ethyl acetate.
Dark green solid, mp >300 oC, (162.7 mg, 46.8 % chemical yield). FT-IR (ATR System, cm-
1): 3059, 2769, 2323, 2166, 2050, 1980, 1713, 1657, 1591, 1502, 1468, 1392, 1360, 1334,

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1309, 1260, 1226, 1158, 1090, 1043, 1013, 943, 829, 747, 693. 1H NMR (300 MHz, DMSO-
d6) δ8.48-8.42 (m, 4H), 8.00-7.88 (m, 12H), 7.46-7.35(m, 22H), 7.25-7.19 (m, 14H).MALDI-
TOF MS: m/z [M]+ calcd. ForC84H52N12O4Zn : 1356.35; found [M+4H]+1360.4.Anal. Calc.
for C, 74.25; H, 3.86; N, 12.37; O, 4.71; Zn, 4.81. Found: C, 74.28; H, 3.89; N, 12.32 %.
2.4.4. Synthesis of Cobalt phthalocyanine, Pc-7
5 (300 mg, 0.92 mmol) was dissolved in the 15 mL mixture of DMEA/DMF (1:2). Cobalt(II)
acetate tetrahydrate (57 mg, 0.23 mmol) was added to this stirring mixture then refluxed at
o
160 C under the nitrogen atmosphere for 24 h. Reaction was finished after TLC controlling.
Then the reaction mixture was poured into the mixture of methanol water (1:1) to stop the
reaction. Obtained dark green solid was dried under vacuum and columned by hexane : ethyl
acetate.Dark green solid, mp >300 oC, (146 mg, 46.5% chemical yield). FT-IR (ATR System,
cm-1):3058, 2942, 2816, 2768, 1715, 1592, 1524, 1503, 1468, 1405, 1361, 1332, 1306, 1261,
1228, 1158, 1093, 1057, 1012, 975, 955, 878, 828, 751, 692, 633. MALDI-TOF MS: m/z [M]+
calcd. ForC84H52N12O4Co : 1351.36; found [M+4H]+1355.4. Anal. Calc. For C, 74.60; H,
3.88; Co, 4.36; N, 12.43; O, 4.73; Co, 4.36. Found: C, 74.64; H, 3.91; N, 9.21 %.
3. Results and Discussion
3.1. Synthesis
The phthalocyanine literature shows the solubility enhancement and the aggregation
preventing in organic media or water the bulky substituents can be used as peripherally or
non-peripherally. Besides the changing of the metal in the phthalocyanine center affects the
solubility of the phthalocyanines [1,30]. We used in this research a basic schiff base 3 as
bulky substituent synthesized from 4-hydroxybenzaldehyde and aniline in methanol.The
reaction has given 74.1% yield. Then the novel imine derivated phthalonitrile 5 was obtained
via the SNAr type substitution reaction between imine 3 and 4-nitrophthalonitrile 4, after the
column chromatography isolation chemical yield was calculated as 59.3% (Scheme 1).
Moreover these imine derivated phthalocyanines are newly discovered for synthesis and
application. As known schiff bases are common studied molecule group in literature. They
have been used for metal sensing application in many papers [31,36]. They have big potential
for metal sensing by fluorescence spectroscopy. Derivatization of metallo Pcs with imines
will give solubility and opportunity of metal sensing. I have reported the redox and
spectroelectrochemistry. Besides I hace studşed the application as catalyst in the oxidation of

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2-mercaptoethanol. These phthlocyanines Pc-6 and Pc-7 have never been metioned in the
literature.
Scheme 1.
1
13
The molecular structures of 3 and 5 are described on the basis of H and C NMR spectra
and approved by FT-IR spectra. The obtained phthalonitrile 5 was used for synthesis of
metallo phthalocyanines Pc-6 and Pc-7. In the synthetic routes of Pcs Zn(OAc)2.2H2O and
Co(OAc)2.4H2O salts were used to give center ions to Pcs recpectiely Zn+2 and Co+2 in the
cyclotetramerization reaction of 5, using DMEA as the catalyst at high temperature, an
1
isomeric mixture of the desired metallo Pcs Pc-6 and Pc-7 as expected (Scheme 2). The H
NMR spectra of Pc-6 was received in CDCl3. Pc-6 is soluble in both CHCl3 and DMSO, so
1
the H NMR spectra for Pc-6 was carried out in CDCl3. Pc-7 is well soluble in CHCl3,
DMSO and DMF. The structures of novel Pc compunds Pc-6 and Pc-7 were characterized by
IR, UV, 1H and 13C NMR, MALDI-TOF techniques.
Scheme 2.
3.1. Structure Elucidation
The FT-IR spectra of all synthesized species shows clearly that the desired products was
achieved in all steps as intended. The band viewed at 1611 cm-1 was attributed to C=N imine
bonds stretching vibration of compound 3. This band shifts to 1626 cm-1 in the compound 5
beacuse of extra aromatic ring in the molecule. After the formation of phthalocyanine this
bands shifts to 1657 cm-1 for Pc-6 and 1715 cm-1 for Pc-7. The FT-IR spectra of 5 gives us
the specific information on the synthesize of imine derivated phthalonitrile shows the
characteristic single band at 2229 cm-1 which can be referred to the triple bond of nitrile.
Figure 1.
The strong characteristic single band at 2229 cm-1 which is referable to the vibration of triple
bond, CN, was seemed clearly. The disappearance of this single band at 2229 cm-1 in the FT-
IR spectrum of both Pc-6 and Pc-7 have been referred as a prof of cyclotetramerization of
monomer 5. The other bands under 2000 cm-1 has not annoying changes. Absorption bands
at3059, 2769, 2323, 2166, 2050, 1980, 1713, 1657, 1591, 1502, 1468, 1392, 1360, 1334,
1309, 1260, 1226, 1158, 1090, 1043, 1013, 943, 829, 747, 693cm-1 are observed for Pc-6;
Theese bands can be attributed to phthalocyanine skeletal vibrations [28,51] Pc-7 also shows

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very similar peaks between 3058-633 cm-1. Because of having aromatic structures of 3 and 5,
the NMR spectrums of 3 and 5 have peaks in between 6-8.5 ppm, similar to starting
1
phthalonitriles. The H-NMR spectra phthalocyanine, Pc-6, shows the peaks in aromatic
region with small chemical shift differences. The mass spectra of phthalocyanines, Pc-6 and
Pc-7, were also taken. Molecular ion peaks are identified 1360.4 as the [M+4H]+ for Pc-6
and 1355.4 as the [M+4H]+ for Pc-7. In the mass spectrum of compounds Pc-6 and Pc-7 the
presence of the molecular ion peaks at m/z = 1360.4 [M+4H]+ and 1355.4 [M+4H]+
respectively, clearly indicates the formation of the proposed structures in scheme 1 and 2.
3.2. UV-Vis absorption spectra
Chloroform was used as organic solvent for recording the UV-Visible spectra of Pc-6 and Pc-
7 over a vide range between 10-5 and 10-4 M.The electronic absorption spectra in the range of
300-750 nm for both Pcs, Pc-6 and Pc-7, can be seen in figure 2 and figure 3 respectively. All
of the absorption spectra shows typical Soret band around 330 nm for both Pc-6 and Pc-7.
Figure 1 and 2 shows typical non-aggregated phthalocyanines. In the concetration studies of
phthlocyanine Pc-6 (figure 1 inset) linear regression coefficient, R2, was found as 0.9967.
This is nearly lineer line and shows that this phthalocyanine has no aggregation behaviour.
Figure 2.
Figure 2 shows that Pc-6 has a strong Q band at 679 nm in chloroform having a shoulder at
643 nmwith a vibronic band at 609 nmnm and also a Soret band peaking at 335 nm. On the
other side figure 3 shows also a strong Q band at 666 nm in chloroform having a shoulder at
636 nmwith a vibronic band at 601 nm and also a Soret band peaking at 317 nm.
Figure 3.
Both of the phthalocyanines, Pc-6 and Pc-7, show non-aggregation behaviour. So both Pcs
are able to use for appropriate applications.
3.3. Cyclic voltammetric measurements
Figure 4.

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Cyclic voltammograms (CV’s) were taken with Reference 300 potentiostat/galvanostat. A
three electrodes system having a Pt working alectrode, Pt counter electrode and Ag/AgCl
reference electrode was operated. Extra pure dimethylsulfoxide was used as solvent for
phthalocyanines and 0,1 mol/L tetra-n-butylammoniumtetrafluoroborate (TBABF4, 99%) was
used as the supporting electrolyte. Figure 4 shows CV responses in DMSO/TBABF4 for Pc-6
and Pc-7. Figure 4 (a) shows that Pc-6, has twoirreversible reduction reactions, R1 at -0.47 V
and R2 at -0.80 V. Figure 4 (b) shows that Pc-7 has only one reduction reaction, R3 at -0.84 V.
3.4. Spectroelectrochemistry
Optically transparent thin-layer electrode (OTTLE) cell kit was used in order to determine the
nature of the redox processes in spectroelectrochemical studies.
Figure 5.
Pc-6 has a strong Q band at 680 nm in DMSO having a shoulder at 647 nmwith a vibronic
band at 610 nm and also a Soret band peaking at 335 nm. Figure 5 shows in-situ UV-Visible
spectral changes when the reduction potential at -0.47 V (R1) for Pc-6. During oxidation of
the constant potential at -0.47 V (vs Ag/AgCl reference electrode) the entire band of
absorption is reduced without a new band formed. Such behavior can be interpreted as
complex undergoes decomposition immediately after the ring oxidation.
Figure 6.
Figure 6 shows UV-Visible spectral changes when the reduction potential at -0.80 V for Pc-6.
There is no shift of the Q band. During oxidation at the constant potential at -0.80 V (R2) (vs
Ag/AgCl reference electrode) the entire band of absorption is reduced without a new band
formed. Such behavior can be interpreted to undergo decomposition of the complex
immediately after the ring oxidation of the complex.
Figure 7.
Pc-7 has a strong Q band at 680 nm in DMSO having no shoulder with a vibronic band at 600
nm and also a Soret band peaking at 332 nm. Figure 7 shows in-situ UV-Visible spectral
changes when the reduction potential at -0.84 V (R3) for Pc-7. Isosbestic points were
observed at 537 nm, 672 nm and 730 nm. It is well known that an isosbestic point occurs
when you overlay spectra collected overtime, indicates that there is a change from one state to
another. The absorption spectrums observed at 680 nm at Q band in the beginning of the
constant electrolysis are indications that any type of aggregation does not occur. These

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spectral changes walking with the formation of a clearly defined isosbectic points can be
stated that due to the ring based reduction. Therefore R3 pair can be attributed to ligand-based
reduction of Pc's. Any in situ spectroelectrochemical process in R1, R2 and R3 has not undergo
to shift of the Q band. This is due to stabilization of the highest occupied molecular orbital
(HOMO) in MPc complexes relative to the lowest unoccupied molecular orbital (LUMO)
[47].
3.5. Catalytic oxidation of 2-mercaptoethanol
The catalytic activity of Co(II)phthalocyanines on the oxidation of 2-mercaptoethanol is well
known application [48-50]. Pc-7 is monomolecular and non-aggregated as seen in chapters
3.2, 3.3 and 3.4. Co(II)Pc coordinate the thiolate anion RS- generated by NaOH and O2 on two
axial sides of the central Co(II) in Pc-7. Then the electron transfer from the thiolate to oxygen
via central Co(II) occurs disulfide. The reaction between 2-mercaptoethanol and oxygen can
be seen in equation (1).
4R-S- + O2 → R-S-S-R + 4OH-
(1)
The catalytic ratio of 2-mercaptoethanol and phthalocyanine (thiol/catalyst=14000). This
reaction need a basic media. When a small amount of NaOH solution was added to the
reaction mixture the thiol (RSH) will produce immediately thiolate (RS-). Then the Co(II)Pc
will start to catalyse the oxidation of 2-mercaptoethanol by oxygen. TON, initial reaction rate
and the oxygen consumption was calculated as 18.6, 0.34, 2.75 recpectively and oxygen
consumption over time is seen on figure 8.
Figure 8.
Conclusion
In conclusion, novel Zn(II) and Co(II) phthalocyanines which are substituted with imine
carrying four schiff bases on the peripheral positions have been synthesized and characterized.
In our synthetic route, the schiff base group was synthesized firstly in the methanol. Then 4-
nitrophthalonitrile was bounded to synthesized group via SNAr type substitution reaction. The
well known Pc synthesize method was used for the direct synthesize of both Pc-6 and Pc-7
phthalocyanines. The structures of all compounds synthesized have been fully characterized

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1
by using FT-IR, H NMR, 13C NMR, MALDI-TOF MS, and UV-vis spectroscopic
techniques.
Electronic absorption spectra showed that both Pcs are nonaggregable molecules and also
well solubles common organic solvents such as dichloromethane, chloroform, THF, DMSO
and DMF. Cyclic voltammograms give two reduction reaction for Pc-6 and one reduction
reaction for Pc-7. The spectroelectrochemical investigation shows the ring based reduction
potential for MPc’s. Pc-6 undergo decomposition of the complex immediately after the ring
oxidation in both reduction potential. Pc-7 cobalt(II)phthalocyanine was investigated as
catalyst in the catalytic oxidation of 2-mercaptoethanol. The catalytic oxidation of 2-
mercaptoethanol is a widely studied reaction for the detection of catalytic activity. Turnover
number, initial reaction rate and the oxygen consumption was found in the catalytic oxidation
of 2-mercaptoethanol as 18.6, 0.34, 2.75 recpectively.
Acknowledgments
This research is funded by Sakarya University Scientific Research Projects Unit (BAPK:
2015-02-04-002).
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Scheme 1. Synthetic route for the imin 3, phthalonitrile 5 and and target Pc scaffolds
Scheme 2. Synthesis of target phthalocyanines Pc-6 and Pc-7
Figure 1. FTIR spectrums of componds 3, 5, Pc-6, Pc-7.
Figure 2. UV-Visible absorption spectra of Zinc phthalocyanine, Pc-6
Figure 3. UV-Visible absorption spectra of Cobalt phthalocyanine, Pc-7
Figure 4. CV’s of (a)Pc-6 and (b)Pc-7 recorded at 100 mV/s scan rate on a Pt working
electrode in DMSO/TBAB
Figure 5. UV-Vis in-situ spectral changes of complex Pc-6 in DMSO containing 0.1 M
TBABF4 observed during application of controlled potential at potential of the -0.47V.
Figure 6. UV-Vis in-situ spectral changes of complex Pc-6in DMSO containing 0.1 M
TBABF4 observed during application of controlled potential at potential of the -0.80 V.
Figure 7. UV-Vis spectral changes of complex Pc-7in DMSO containing 0.1 M TBABF4
observed during application of controlled potential, R3 at -0.84 V.
Figure 8. Oxygen consumption in the reaction of catalytic oxidation of 2-mercaptoethanol by
Co(II)Pc as catalyst in THF.

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Scheme 1.

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Scheme 2.

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Figure 1.

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Figure 2.

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Figure 3.

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Figure 4.

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Figure 5.

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Figure 6.

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Figure 7.

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Figure 8.
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The synthesis of new schiff base substituted metallophthalocyanines.
Redox behavior of schiff base substituted metallophthalocyanines.
Synthesize and characterization of phthalocyanines bearing schiff bases.
Spectroelectrochemistry of schiff base substituted phthalocyanine.
The catalytic activity of schiff base substituted phthalocyanine for mercaptan oxidation.