Substituted Co(II) and Cu(II) metallophthalocyanines from new Schiff base containing pyrrole units: Synthesis, characterization and investigation of photocatalytic activity on 2,3-dichlorophenol oxidation

Article abstract of DOI:10.1007/s10847-019-00949-z

In this article, novel Schiff base compound 1 bearing pyrrole moiety has been synthesized from the reaction of 1-hydroxybenzaldehyde with 1,2-aminophenylpyrrole for the first time. The cobalt phthalocyanine and copper phthalocyanine (3–4) were prepared by

Full text of DOI:10.1007/s10847-019-00949-z

Journal of Inclusion Phenomena and Macrocyclic Chemistry
https://doi.org/10.1007/s10847-019-00949-z
ORIGINAL ARTICLE
Substituted Co(II) and Cu(II) metallophthalocyanines from new
Schif base containing pyrrole units: Synthesis, characterization
and investigation of photocatalytic activity on 2,3‑dichlorophenol
oxidation
Ayse Aktas Kamiloglu1 · Ece Tugba Saka2 · Irfan Acar3
Received: 11 July 2019 / Accepted: 4 October 2019
© The Author(s) 2019
Abstract
In this article, novel Schif base compound 1 bearing pyrrole moiety has been synthesized from the reaction of 1-hydroxy-
benzaldehyde with 1,2-aminophenylpyrrole for the frst time. The cobalt phthalocyanine and copper phthalocyanine (3–4)
were prepared by the cyclotetramerization of the novel phthalonitrile compound 2 and the corresponding metal salts. The
new phthalonitrile compound 2 was synthesized by the reaction between 4-((E)-{[2-(1H-pyrro-1-yl)phenyl]imino}methyl)
phenol 1 and 4-nitrophthalonitrile in DMF. The all new compounds (1–4) have been characterized by FT-IR spectroscopy,
1H-NMR/13C-NMR, mass, UV–Vis spectroscopy techniques and elemental analysis (for metallophthalocyanines). Chlorine-
bearing phenols are of a class of pollutants. They have been regarded as a potential risk to environment and human health. It
is important to advanced efective techniques to remove chlorinated phenols in wastewater. For this purpose, we investigated
that diferent parameters infuenced the photooxidation process were determined and 2,3-dichlorophenol oxidize to the less
harmfull products with high conversion and yield in the presence of Cu(II) and Co(II) phthalocyanine catalysts.
Keywords Metallophthalocyanine · Schif base · Pyrrole · 2,3-Dichlorophenol · Photocatalysis
Introduction
chemical sensors, catalysis, oxidation, electrochromic
agents, semiconductors, photosensitizers for photodynamic
cancer therapy (PDT), liquid crystals, nonlinear optics and
solar energy conversion [1–5]. The chemical properties of
the substitutent groups attached to the peripheral positions
of phthalocyanine signifcantly afect the properties of Pcs,
such as their solubility, aggregation, electronic absorption
and photocatalysis properties [6].
Phthalocyanines compounds (Pcs) have been consid-
ered to be promising nominee due to their unique physi-
cal, electronic and optical properties. Except for their use
as dyes, Pcs have been broadly studied because they have
been applied to many scientifc feld applications such as
Pyrrole itself is not naturally occurring. A lot of bioac-
tive natural products (such as vitamin B12, bilirubin, por-
phyrins and chlorophyll) and synthetic drugs contain a
pyrrole moiety as their skeleton [7, 8]. They were found
to possess a wide variety of biological activities such as
anticancer, antifungal, antibacterial, anti-infammatory and
antioxidants [9–16]. Schif bases derived bearing pyrrole
moiety are effective many areas. Also, Schiff bases are
known great interest due to their biological properties [17].
The mentioned facts about pyrrole group encouraged us to
synthesize of new Schif base bearing pyrrole moiety and its
metallophthalocyanines.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s10847-019-00949-z) contains
supplementary material, which is available to authorized users.
* Ayse Aktas Kamiloglu
ayse_aktas_kamiloglu@artvin.edu.tr;
ayse_aktas@hotmail.com
1
Artvin Vocational School, Artvin Çoruh University,
08100 Artvin, Turkey
2
Department of Chemistry, Faculty of Science, Karadeniz
Technical University, 61080 Trabzon, Turkey
3
Department of Energy Systems Engineering, Faculty
of Technology, Karadeniz Technical University,
61830 Trabzon, Turkey
Vol.:(0123456789)
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Water contamination with chlorinated organic com-
pounds have been informed as an environmental threat [18].
Chlorophenols have been used in wood preservers, fungi-
cides, dyes, herbicides and drugs [19]. Excessive chloro-
phenol consumption of the industry leads to large amounts
of water pollution. Most of chlorophenols are extremely
mutagenic, carcinogenic, toxic and they are high persis-
tence and bioaccumulation in the environment [19, 20].
Therefore, chlorophenols have been listed as the important
priority contaminants in many countries. They have great
potential risks to human health [21, 22]. The conventional
treatment processes such as focculation, adsorption, pho-
tocatalysts, membrane fltration and biodegradation are not
very efective in decreasing the risk of chlorophenols in the
environment because of the stable molecular structure and
biotoxicity of chlorophenols, [23, 24]. Hence, researchers
are still working to develop more efective technology for
chlorophenols treatment.
135.77, 130.49, 129.48, 129.32, 129.12, 128.06, 126.87,
126.02, 124.53, 116.63, 116.38, 115.74, 114.89, 114.85,
109.22. MS (ESI), (m/z): Calculated: 262.30; Found: 261.26
[M − H]+.
Synthesis of 4‑{4‑((E)‑{[2‑(1H‑pyrroll‑1‑yl)phenyl]imino}
methyl)phenoxy] phthalonitrile (2)
Compound 1 (0.6 g, 2.29 mmol) and 4-nitrophthalonitrile
(0.4 g, 2.29 mmol) were dissolved in dry DMF (10 mL)
and the solution was stirred at 60 °C. Then, powdered dry
K2CO3 (0.95 g, 6.87 mmol) was added to the system in eight
equal portions over 2 h. The mixture was stirred under N2
at 60 °C for 5 days. After fve days, the reaction mixture
was poured into ice-water and stirred at room temperature
to yield a product. The mixture was fltered and washed with
water then dried in vacuum and recrystallized from ethanol
to pink product. Yield: 0.4 g (45%). IR (ATR), νmax/cm−1:
3095 (Ar–H), 2232 (C≡N), 1592–1561 (C=N), 1486-1475
(C=C), 1425, 1375, 1280, 1252, 1208, 1098, 1043, 933, 837,
750, 716. 1H-NMR. (CDCl3), (δ:ppm): 8.58 (s, 1H, HC=N),
8.35 (d, 1H, Ar–H), 8.17-8.13 (t, 4H, Ar–H), 7.96–7.94 (m,
2H, Ar–H), 7.65–7.61 (m, 4H, Ar–H), 7.40–7.38 (d, 2H,
Ar–H), 7.10–7.01 (m, 2H, Ar–H). 13C-NMR. (CDCl3),
(δ:ppm): 161.01, 155.79, 152.53, 136.87, 135.89, 135.52,
131.26, 129.99, 128.47, 127.16, 126.04, 124.52, 123.75,
123.18, 120.60, 117.30, 117.15, 116.36, 115.86, 115.23,
114.84, 109.20, 108.93. MS (ESI), (m/z): Calculated:
388.42; Found: 387.19 [M – H]+.
In this work, the synthesis, characterization and struc-
tural examination of Schif base bearing pyrrole group 1,
phthalonitrile 2 and Co(II) and Cu(II) Pcs (3–4) contain-
ing 4-((E)-{[2-(1H-pyrro-1-yl)phenyl]imino}methyl)phenol
groups were described. Furthermore, photocatalytic activ-
ity on 2,3-Dichlorophenol oxidation of the phthalocyanines
were investigated.
Experimental
Materials
General procedure for synthesis of metallophthalocyanines
(3, 4)
The used materials and equipments were supplied as sup-
plementary information.
Substituted phthalonitrile 2 (0.1 gr, 0.26 mmol) and for met-
allophthalocyanines corresponding anhydrous metal salts
[(CoCl2 (17 mg, 0.13 mmol); CuCl2 (17.40 mg, 0.13 mmol)]
were dissolved in 1.5 mL of DMAE. Then the temperature
was raised to 160 °C and stirred for 24 h under nitrogen
atmosphere. Methanol was added to the medium and the
green raw products were fltrated and washed with hot etha-
nol, methanol and diethyl ether. The green product was puri-
fed on alümina column with chloroform:methanol (10:1)
for compound 3, (10:1) for compound 4 solvent system as
eluent. Spectral data of these products were given below.
Synthesis
Synthesis of 4‑((E)‑{[2‑(1H‑pyrro‑1‑yl)phenyl]imino}methyl)
phenol (1)
1-Hydroxybenzaldehyde (0.77 g, 0.63 mmol) was dissolved
50 mL of alcohol under nitrogen gas. 1,2-Aminophenylpyr-
role (1 g, 0.63 mmol) was added this solution with stirring
for 30 min and 6 drops of CH3COOH were added in this
mixture. The reaction mixture was refuxed under nitro-
gen for 24 h. After the mixture was cooled, the solvent was
removed under vacuum and recrystallized from methanol to
Cobalt(II) phthalocyanine (3) Yield: 25 mg (11%).
mp:>300 °C. IR (ATR) νmax/cm−1: 3063 (Ar–CH), 1597–
1504 (C=N), 1472–1462 (C=C), 1365, 1227, 1160, 1095,
929, 832, 750, 712. UV–Vis (THF): λmax, nm (log ε): 663
(5.06), 601 (4.55), 330 (4.23). MALDI-TOF–MS m/z:
Calculated:1610.93; Found: 1611.07 [M+H]+. Elemental
Analysis, Anal, calc. for C100H64N16O4Co: C, 74.49; H,
3.97; N, 13.91; Found: C, 72.40; H, 2.96; N, 12.00%.
light pink product. Yield: 0.58 g (35.72%). IR (ATR), νmax
/
cm−1: 3343 (Aliph-OH), 3056 (Ar–H), 1608–1592 (C=N),
1512 (C=C), 1474, 1336, 1284, 1247, 1160, 1111, 832, 754,
695. 1H-NMR. (CDCl3), (δ:ppm): 9.91 (s, 1H, Ph-OH), 8.51-
8.50 (m, 1H, HC=N), 8.30–8.27 (m, 1H, Ar–H), 7.91–7.88
(m, 4H, Ar–H), 7.59–7.46 (m, 2H, Ar–H), 7.05-6.94 (m,
5H, Ar–H). 13C-NMR. (CDCl3), (δ:ppm): 159.30, 153.47,
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Copper(II) phthalocyanine (4) Yield: 35 mg (17%).
mp:>300 °C. IR (ATR) νmax/cm−1: 3056 (Ar–CH), 1597–
1504 (C=N), 1474–1423 (C=C), 1320, 1229, 1161, 1097,
929, 835, 753, 715. UV–Vis (THF): λmax, nm (log ε): 676
(4.98), 608 (4.64), 340 (4.97). MALDI-TOF–MS m/z: Cal-
culated: 1615.55; Found: 1616.32 [M+H]+. Elemental
Analysis, Anal, calc. for C100H64N16O4Cu: C, 74.29; H,
3.96; N, 13.87; Found: C, 70.36; H, 4.35; N, 12.82.
supported the structure. The mass spectra of compound 1
confrmed the structure proposed, with the molecular ion at
261.26 [M−H]+.
The synthesis of 4-{4-((E)-{[2-(1H-pyrroll-1-yl)phe-
nyl]imino}methyl)phenoxy] phthalonitrile 2 was obtained
through base-catalyzed aromatic displacement of 4-nitroph-
thalonitrile with schif base compound 1 using K2CO3 as
the base in dry DMF. In the IR spectrum of phthalonitrile
compound 2 was clearly verifed with the disappearance of
the OH group of 1 and the presence of of C≡N group by
1
General procedure for the photooxidation of substituted
phenols
the sharp stretching bands at 2232 cm−1. In the H-NMR
spectrum of compound 2 at δ = 9.91 ppm (Ph-OH signal)
was disappeared (Fig. 3). In the 13C-NMR spectrum of com-
pound 2 indicated the presence of nitrile carbon atom (C≡N)
at δ = 115.86–115.23 ppm. In the mass spectra of phtha-
lonitrile compound 2, the molecular ion peak was observed
at m/z: 387.19 [M−H]+, confrmed the proposed chemical
structure.
Experiments were carried out in a photocatalytic reac-
tor equipped with stirrer and 18 pieces 8 W UV lamp.
The solution of 2,3-dichlorophenol and catalyst in sol-
vent was degassed. A mixture of 2,3-dichlorophenol
(3.72 × 10−3 mol), catalyst (3.10 × 10−6 mol), oxidant
(2.48 × 10−3 mol) and solvent (0.01 L) was stirred in a
reaction vessel for 1 h at room temperature. The samples
(0.5 mL) were taken at certain time intervals. Each sam-
ple was injected at least twice in the GC, 1 µL each time.
Formation of products and consumption of substrates were
monitored by GC. The structure of the reaction products was
confrmed by 1H-NMR spectroscopy.
Cyclotetramerization of compound 2 to the peripherally
tetra-substituted metallophthalocyanines (3–4) were accom-
plished in the presence of metal salts (CoCl2 and CuCl2) at
160 °C in DMAE in 24 h under inert atmosphere. In the IR
spectra, the formation of metallophthalocyanines (3–4) was
clearly confrmed by the disappearance of the C≡N band.
The 1H-NMR spectra of CoPc and CuPc could not be deter-
mined owing to the paramagnetic nature [25]. The molecular
ion peaks are identifed at m/z=1611.07 [M+H]+ for CoPc
3 (Fig. 4) and 1616.32 [M+H]+ for CuPc 4.
Results and discussion
Phthalocyanine complexes have two strong characteristic
region in the UV–Vis spectum; B band is at 300–500 nm
and the more energetic absorption, known as the Q band,
near 600–700 nm [25]. The UV–Vis absorption spectrum of
synthesized cobalt and copper phthalocyanines (3 and 4) in
THF at 12×10−6 M concentration was shown Fig. 5. In the
UV–Vis absorption spectra of 3 and 4 Q band absorptions
were observed at 663/601 (corresponds to degenerate D4h
symmetry) and 676/608 nm, respectively. Also in the B band
absorptions were observed at 330 and 340 nm, respectively.
The metallophthalocyanines 3 and 4 have the same
peripherally but they have diferent metal ions in core. The
CuPc 4 showed red-shifted Q band comparison to the CoPc
3 phthalocyanine complex. The Q band intense of phthalo-
cyanines 3 and 4 were observed in CoPc>CuPc (Fig. 5).
Synthesis and characterization
The general synthetic pathway for the synthesis of schif base
compound 1, phthalonitrile derivative 2 and its cobalt(II)
3, copper(II) 4 phthalocyanine complexes were given in
Fig. 1. All novel compounds (1–4) were fully characterized
by IR, 1H-NMR/13C-NMR (for compounds 1–2), UV–Vis
(for compounds 3–4), MS spectral data and elemental analy-
sis for metallophthalocyanines. 4-((E)-{[2-(1H-pyrro-1-yl)
phenyl]imino}methyl)phenol 1 was prepared through acid
catalyzed reaction of 1-hydroxybenzaldehyde with 1,2-ami-
nophenylpyrrole in alcohol. The formation of compound 1
was confrmed by the combination of spectroscopic data.
The main feature characterizing its IR spectra is the presence
of OH band at 3343 cm−1, the disappearance of the band
corresponding to NH2 and C=O groups and the detection
of a strong C=N stretching band at 1608–1592 cm−1 evi-
denced the formation of the schif base 1. In the 1H NMR
of the compound 1 revealed a singlet at δ = 9.91 ppm to
the phenolic OH group, another signal characterized at the
1H-NMR spectrum at δ=8.51 corresponding to the imine
(–N=CH) group (Fig. 2). The characteristic 13C-NMR signal
of at δ: 159.30 ppm (C-imine) and the other signals (Ar–C)
Catalytic studies
Oxidation of phenolic compounds with complex 3 and 4
The catalytic properties of Co(II) and Cu(II) phthalocya-
nine complexes were investigated for the photooxidation
of 2,3-dichlorophenol. The oxidation reaction results were
given in Table 1. All experiments maintained 1 h oxidant
and auxiliary chemicals on the conversion and yields were
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 1 The synthesis route of
compounds 1–4
investigated. The blank reactions were carried out (using no
catalysts or oxidants) and there were no product detectable
(Table 1). It is proved that presence of the catalyst and oxi-
dant are essential for the oxidation. The main products was
determined as 2,3-dihydroxy-1,4-benzoquinone and the side
product was determined as 2,3-dichloroquinol in the oxida-
tion of 2,3-dichlorophenol photooxidation reaction (Fig. 6).
After the photocatalytic studies, the photodegradation
amount of 2,3-dichlorophenol was calculated with the equa-
tion below [26].
X(t) = Co − C(t)∕Co
In the equation above, X(t) is the molar fraction of
2,3-dichlorophenol, Co is the frst concentration and C(t) is
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 2 1H-NMR spectrum of compound 1
Fig. 3 1H NMR spectrum of phthalonitrile compound 2
the concentration of 2,3-dichlorophenol as a function of illu-
mination time. This equation shows a similar profle with the
photocatalytic degradation of the other dyestufs [26–28].
For this purpose, 100 mL of 0.025 M 2,3-dichlorophenol
solution and 5 mg of solid catalyst and oxidant (H2O2)
were reacted in a photoreactor for 1 h under visible light.
During the photocatalytic reaction, all samples from tak-
ing reaction medium were dilluted with dichloromethane
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 4 MALDI TOF MS spectrum of CoPc 3
electron-withdrawing properties) catalyzes the reactions of
thiourea and N,N′-dimethylthiourea with oxygen [31, 32].
The reaction occurs under mild conditions to form the cor-
responding urea and sulfur in high yield. In this work, we
studied the catalytic oxidation reactions of 2,3-dichlorophe-
nol with diferent oxygen sources and achieved to activate
oxygen.
To determine oxygen source effect, TBHP, H2O2,
m-CPBA were used as oxidant. The results in Table 1
showed that H2O2 was the best oxidant for 2,3-dichloro-
phenol oxidation in the presence of cobat phthalocyanine
3. Also, TBHP and m-CPBA can serve as an oxidant. But
low conversion was observed for both CoPc 3 and CuPc 4.
The reaction color changed from light blue to brown when
we added TBHP or m-CPBA in the reaction media. This
clue expresess that the complex 3 was degraded immediately
with TBHP or m-CPBA [33, 34]. When H2O2 was used as
an oxygen source, reaction color was bright blue color for
30 min and then changed to yellow and light yellow at the
end. This observation proved that phthalocyanine catalyst
can be more photocatalytically active with H2O2 as an oxy-
gen source in this catalytical process. Figure 8 shows the
relationship between oxidant type and the total conversion.
To fnd the optimal reaction conditions, oxidant/catalyst
ratio was tested in 2,3-dichlorophenol oxidation. When the
oxidant/catalyst ratio was increased from 400/1 to 1200/1,
the rate of the reaction increased. In contrast, while the cata-
lytic oxidation was processing from 1200/1 to 1800/1, the
conversion inclined to decreasing. At this stage, it is possible
Fig. 5 UV-vis absorption spectra changes of CoPc and CuPc in THF
and injected into the injection port of a GC apparatus, with
phenol being the internal reference in this case. As a result,
we have observed that a great portion of 2,3-dichlorophe-
nol has been degraded and after 60 min, the degradation
rate has been fxed. Data about photocatalytic oxidation of
2,3-dichlorophenol that was sensitized with complex 3 under
visible light were presented in Fig. 7.
Oxygen activation in oxidation reactions is a chal-
lenging problem of modern chemistry and biochemistry.
Co(II) complexes are involved in the one-electron reduc-
tion of oxygen to form the superoxo (Co(III)–) or peroxo
derivatives (Co(III)– –Co(III)) [29, 30]. V.N. Shishkin
et al. reported that the cobalt complex with 4-octasulfophe-
nyltetrapyrazinoporphyrazine (a ligand with pronounced
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Table 1 Selective oxidation
of 2,3-dichlorophenol with
catalysts 3 and 4 using diferent
oxidant and temperature
Subs./Ox./Cat
Oxidant
Conversion
(%)
Selectivitya
(%)
TON
TOF (h−1
)
3
4
3
4
3
4
3
4
400/800/1
800/800/1
H2O2
H2O2
H2O2
H2O2
H2O2
m-CPBA
TBHP
H2O2
49
65
97
90
75
48
33
–
28
49
83
78
56
51
18
–
51
88
90
88
66
61
49
–
43
68
90
80
63
58
41
–
196
520
1164
1440
1350
576
396
–
112
392
996
1248
1008
612
227
–
196
520
1164
1440
1350
576
396
–
112
392
996
1248
1008
612
227
–
1200/800/1
1600/800/1
1800/800/1
1200/800/1
1200/800/1
600/800/free cat.
600/free ox./1
H2O2
–
–
–
–
–
–
–
–
TON=mole of product/mole of catalyst
TOF=mole of product/mole of catalyst x time
Conversion was determined by GC
Reaction conditions: 1200/800/1: 3.72×10−3 mol)/2.48×10−3 mol/3.10×10−6 mol
aSelectivity of 2,3-dihydroxy-1,4-benzoquinone Reaction time=1 h
Fig. 6 The oxidation products
of 2,3-dichlorophenol
Fig. 8 The oxidant efect on 2,3-dichlorophenol oxidation [Reaction
conditions: 2,3-dichlorophenol (3.72×10−3 mol), Co(II)Pc and Cu(II)
Pc (3.10×10−6 mol), oxidant (2.48×10−3 mol), DMF (0.01 L), 1 h at
room temperature]
Fig. 7 The photocatalytic oxidation of 2,3-dichlorophenol with near
visible light irradiation CoPc 3 and in dark
that the coordination around the cobalt ion can change and
produce inactive intermediate species [35].
electronic confguration of central metal atom can change
the catalytic activity of phthalocyanine. The activity of met-
allophthalocyanines in oxidation reaction follows the order
CoPc > CuPc. It is known that the catalytic performance
of transition metal species depends on the outer d-electron
density [34].
We are interested in the nature of the introduced transi-
tion metals that are used in these catalytic works. Consid-
ering metallophthalocyanines are representatives for fat,
π-conjugated carbon systems, their electronic properties are
determined to a large extent by the central metal atom. The
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
In general, the OH groups in the chlorophenol ring are
ortho and para directing with activation, whereas Cl sub-
stituents are ortho and para directing with deactivation.
When the OH radical, an electrophilic reagent, is attacking
2,3-dichlorophenol, it is expected to attack the electron rich
positions and cause to generate major para or ortho substi-
tuted intermediates (2,3-dichloroquinol). The route in Fig. 9
shows that the detected intermediate are all rationalized as
being formed by hydrogen abstraction, followed by para
or ortho hydroxylation of the ring. Hydroxyl radical attack
preferentially the aromatic moiety due to their electrophilic
character to form the hydroxylated compound. The product
are then followed to dechlorinate through the OH attack and
fnally oxidized to quinone [36].
in these literatures and our works, it is inferred that the com-
pound 3 will be interesting catalyst in 2,3-dichlorophenol
photooxidation. The results of previous our works were also
valuble because of the high conversion and selectivity of
phthalocyanine. But in this research it is the frst time to
investigate the photocatalytic activity of newly synthesized
Co(II) 3 and Cu(II) 4 phtalocyanines on 2,3-dichlorophenol
oxidation with high product conversion and selectivity.
Conclusion
In this paper, novel CoPc and CuPc (3–4) which are sub-
stituted with pyrrole carrying four Schiff bases on the
peripheral positions were synthesized. Firstly, the Schif
base ligand 1 was prepared and then novel phthalonitrile
compound 2, starting compound of phthalocyanines, was
synthesized via SN2Ar type substitution reaction. The syn-
thesized compounds have been characterized IR, NMR,
UV–Vis and MS spectroscopies techniques and elemental
analysis. The MPcs 3–4 are highly soluble in most of the
organic solvents and the catalytic activity of 3 and 4 were
examined for the oxidation of 2,3-dichlorophenol using dif-
ferent oxygen sources. The CuPc 4 showed feasible catalytic
activity with 83% and 90% product conversion and selectiv-
ity for 2,3-dichlorophenol photooxidation. The results indi-
cated that the catalyst 3 showed convincing activity for the
Some previously reported catalysts are summarized in
Table 2. Diferent groups substituted cobalt(II), iron(II),
aluminium(III), copper(II) and metal free phthalocyanines
were investigated on photooxidation of diferent pollutants
[37–43]. In the literature, there are quite a few studies about
photocatalytic applications of phthalocyanine on the envi-
ronmental pollutants degradation. Some of them are focused
on get high singlet oxygen quantum yield and efciency
without any measurements of product conversion, selectiv-
itiy, turnover number and turnover frequency. In our previ-
ous work, tetrasubstituted Co(II), Fe(II) and Cu phthalocya-
nine complexes were also studied as catalyst in the oxidation
of phenolic compounds [44–51]. By comparing the catalyst
Fig. 9 The proposed mechanism
OH
OH
OH
of 2,3-dichlorophenol
Cl
Cl
Cl
Cl
Cl
hv /MPc
.
OH
H
.
Cl
H
H
OH
OH
H
OH
OH
OH
OH
Cl
OH
OH
OH
Cl
2
2
Cl
e-/
H+
+2
O
+2
H+
-2
OH
OH
O
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Table 2 Catalytic activities of
Catalyst
Substrate
Rxn Time
(h)
Rxn Temp.
(oC)
Oxidant Conv.
(%)
References
phthalocyanines towards the
photooxidation of diferent
organic compounds in some
previously reported catalyst
ZnTsPca
FePcb
Methyl orange-Orange G 10 min
Ethyl benzene
Malachite green
2-Mercaptoethanol
nr
rt
nr
rt
rt
27
rt
O2
O2
–
nr
[36]
[37]
[38]
[39]
[40]
[41]
[42]
9 h
30 min
2
1
5
3
>99
99.2
nre
CoTNPcc
CoPcd
–
Metal free Pcf Süfide ion
O2
–
O2
70
CuPcg
4-Nitrophenol
4-Chlorophenol
nrh
CoPci
99.99
ZnPcj
97.05
aZnTs-CoFerrite=2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato
Zn(II)
bFePc-POF=four-branched tetra-amine FePc-porous organic framework
cCoTNPc/SnIn4S8 =Tetranitrocobalt phthalocyanine/ternary chalcogenide
dCoPc=Cobaltphthalocyanine/C60
enr=Turnover number is given as 8.4
fMetal free Pc=Metal free phthalocyanine/TiO2
gCuPc=Copper phthalocyanine/TiO2
hnr=Quantum yield is given as 1.9
iCoPc=2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato cobalt(II)/TiO2
jZnPc=2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato zinc(II)/TiO2
nr not reported
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photooxidation of 2,3-dichlorophenol to the corresponding
2,3-dihydroxy-1,4-benzoquinone as major product in 1 h at
room temperature with the highest conversion, selectivity
and TON (respectively; 97%, 90% and 1164). The optimal
conditions were also determined in 2,3-dichlorophenol oxi-
dation with CoPc 3. All the results indicated that CoPc 3
with catalytic oxidation were efcient and cleaning technol-
ogy for industrial waste application. Transformation envi-
ronmentally harmful phenolic compounds into less harmful
oxidation products by CoPc 3 derivative makes this study
intriguing.
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Acknowledgements The Authors thank to Artvin Çoruh University
6. Guzel, E., Atsay, A., Nalbantoğlu, S., Saki, N., Doğan, A.L., Gül,
A., Koçak, M.B.: Synthesis, characterization and photodynamic
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and Karadeniz Technical University.
Open Access This article is distributed under the terms of the Crea-
tive Commons Attribution 4.0 International License (http://creativeco
mmons.org/licenses/by/4.0/), which permits unrestricted use, distribu-
tion, and reproduction in any medium, provided you give appropriate
credit to the original author(s) and the source, provide a link to the
Creative Commons license, and indicate if changes were made.
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