Synthesis, aggregation, photocatalytical and electrochemical properties of axially 1-benzylpiperidin-4-oxy units substituted silicon phthalocyanine

Article abstract of DOI:10.1016/j.molstruc.2019.126994

Photosensitized catalysis is the initiation of degradation or transformation reactions of molecules using a combination of light and photoactive materials as catalysts. In this work, 1-benzylpiperidin-4-oxy substituted silicone phthalocyanine (SiPc) 3 has been synthesized and characterized with different spectral data and determined catalytic behavior in p-nitrophenol degradation with 1758 turnover number (TON) and 586 turnover frequency (TOF) values. Metallophthalocyanine 3 is soluble in different organic solvents and investigated aggregation behavior in common organic solvents. Electrochemical properties of metallophthalocyanine 3 was defined by using cyclic voltammetry (CV) technique. Silicone phthalocyanine (SiPc) 3 shows one irreversible reduction couple R₁ at ?0.85 V (ΔE_p = 288 mV), one reversible reduction couple R₂ at ?1.54 V (ΔE_p = 95 mV) and one quasi-reversible oxidation couple O₁ at 1.07 V (ΔE_p = 135 mV).

Full text of DOI:10.1016/j.molstruc.2019.126994

Journal of Molecular Structure 1199 (2020) 126994
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, aggregation, photocatalytical and electrochemical
properties of axially 1-benzylpiperidin-4-oxy units substituted silicon
phthalocyanine
Ece Tugba Saka*, Halise Yalazan, Zekeriya Bıyıklıoglu, Halit Kantekin, Kader Tekintas
Department of Chemistry, Karadeniz Technical University, 61080, Trabzon, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Photosensitized catalysis is the initiation of degradation or transformation reactions of molecules using a
combination of light and photoactive materials as catalysts. In this work, 1-benzylpiperidin-4-oxy
substituted silicone phthalocyanine (SiPc) 3 has been synthesized and characterized with different
spectral data and determined catalytic behavior in p-nitrophenol degradation with 1758 turnover
number (TON) and 586 turnover frequency (TOF) values. Metallophthalocyanine 3 is soluble in different
organic solvents and investigated aggregation behavior in common organic solvents. Electrochemical
properties of metallophthalocyanine 3 was defined by using cyclic voltammetry (CV) technique. Silicone
Received 8 May 2019
Received in revised form
24 August 2019
Accepted 26 August 2019
Available online 30 August 2019
Keywords:
Silicon phthalocyanine
Degradation
p-Nitrophenol
Photocatalyst
phthalocyanine (SiPc) 3 shows one irreversible reduction couple R1 at ꢀ0.85 V ( Ep ¼ 288 mV), one
D
reversible reduction couple R2 at ꢀ1.54 V (
1.07 V (
Ep ¼ 135 mV).
D
Ep ¼ 95 mV) and one quasi-reversible oxidation couple O1 at
D
© 2019 Elsevier B.V. All rights reserved.
1. Introduction
such as diethylaminophenoxyethoxy, benzyloxy, alkyne, 6-
hydroxyhexylthio onto the ring system can improve the solubility
of phthalocyanines in water or common organic solvents [22e31].
On the other hand, owing to the hydrophobic nature of the
phthalocyanine ring, phthalocyanines have a strong tendency to
aggregate in solution, which also limits their applications. However
axially disubstituted silicon phthalocyanines are non-aggregated
due to the non-planar substituents issuing from the center metal
atom [32,33]. In order to increase the solubility of silicon phthalo-
cyanines in common organic solvents and applications in different
areas, we have synthesized new axially substituted silicon
phthalocyanine.
In this work, we have synthesized and characterized 1-
benzylpiperidin-4-oxy substituted silicone phthalocyanine.
Axially-substituted silicon phthalocyanines (SiPcs) are of
marvelous interest to scientists because they are generally not able
to aggregate due to their special structural features [34]. Aggrega-
tion behavior of silicon phthalocyanine has been investigated in
different organic solvents. Photocatalytic activity of silicon phtha-
locyanine complex has been investigated in oxidation of p-nitro-
phenol with different oxygen sources, different amounts of catalyst,
TON and TOF values. The electrochemical behavior of silicon
phthalocyanine has also been measured with the cyclic voltam-
metry (CV) and square wave voltammetry (SWV).
Phthalocyanines (Pcs) are a well-established group of synthetic
dyes that have received increased attention of researchers in the
last decades [1e3]. Their high thermal stability, interesting optical,
photophysical, photochemical and electrochemical properties were
used for development of photosensitizers in photodynamic therapy
[4e6], dye-sensitized solar cells [7,8], fluorescence sensors [9,10],
fluorophores [11,12], colorants and materials for optical, electronic
and photo-electronic devices [13,14].
In recent years, catalytic degradation of organic pollutants using
different metal catalysts is attracting many interests [15e19]. Due
to metallophthalocyanines (MPcs) are synthetic molecules and
structurally analogous to porphyrin complexes, they show bio-
inspired chemistry [20,21]. The catalytic properties of metal-
lophthalocyanines depend on the metal atom and structure of the
phthalocyanine moiety. Different metals are inserted in the core of
the phthalocyanine ring to utilize them in specific reactions.
Phthalocyanines show very stinted solubility in most organic
solvents and water, a feature which restrains their applications in
several areas. However the introduction of various substituents
* Corresponding author. Tel.: þ90 462 377 24 92, Fax: þ90 462 325 29 33.
E-mail address: ece_t_saka@hotmail.com (E.T. Saka).
https://doi.org/10.1016/j.molstruc.2019.126994
0022-2860/© 2019 Elsevier B.V. All rights reserved.

2
E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
2. Experimental
2.5. General procedure for the photooxidation of substituted
phenols
2.1. Materials
Experiments were carried out in a photocatalytic reactor
All reactions were carried under a dry nitrogen atmosphere
using Standard Schlenk techniques. All chemicals, solvents, and
reagents were of reagent grade quality and were used as purchased
from commercial sources. All solvents were dried and purified as
described by reported procedure [35]. 4-Nitrophthalonitrile 2 [36]
were prepared according to the literature procedure. p-nitro-
phenol, o-chlorophenol, 2,3-dichlorophenol and p-methoxyphenol
were purchased from Sigma-Aldrich and used without further
purification and chemical treatment.
equipped with stirrer and 18 pieces 8W UV lamp. The solution of p-
nitrophenol compound and catalyst in solvent was degassed. A
mixture of p-nitrophenol compounds (10.85 ꢁ 10ꢀ3 mol), catalyst
(5.43 ꢁ 10ꢀ6 mol, oxidant (2.71 ꢁ 10ꢀ3 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 sample
was injected at least twice in the GC, 1 mL each time. Formation of
products and consumption of substrates were monitored by GC.
The structure of the reaction products was confirmed by 1H NMR
spectroscopy.
2.2. Equipment
3. Results and discussion
The IR spectra were recorded on a PerkinElmer 1600 FT-IR
spectrophotometer using KBr pellets. 1H NMR and 13C NMR
spectra were recorded on a Varian Mercury 400 MHz spectrometer
3.1. Synthesis and characterization
in CDCl3. Chemical shifts were reported (
d
) relative to Me4Si as
The formation of bis(1-benzylpiperidin)-4-oxyphthalocyaninato
silicon(IV) 3 was clearly confirmed by the disappearance of the OH
band at 3330 cmꢀ1 for 2 in the IR spectra of the silicon phthalocy-
anine 3. On the other hand, the characteristic vibrations corre-
sponding to aliphatic eCH stretching at (2946e2884 cmꢀ1) aromatic
eCH peaks at (3062 cmꢀ1) bands were observed for complex 3. In
the 1 H NMR spectra, the phthalocyanine ring proton resonances
appeared as multiplets integrating each as 8H at
internal standard. MALDI-MS of complexes were obtained in
dihydroxybenzoic acid as MALDI matrix using nitrogen laser
accumulating 50 laser shots using Bruker Microflex LT MALDI-TOF
mass spectrometer. Optical spectra in the UVevis region were
recorded with a PerkinElmer Lambda 25 spectrophotometer. GC
Agilent Technologies 7820A equipment (30 m ꢁ 0.32 mm
x
0.50 m DB Wax capillary column, FID detector) was used GC
m
measurements. Photocatalytic experiments were carried out in
photocatalytic reactor. A UV lamp (18 ꢁ 8W) producing 265 nm
near visible light was used for photocatalytic studies.
[(8.96e8.88)e(8.44e8.36) ppm] for the a and b protons, respec-
tively. The other aliphatic and aromatic protons appeared at
7.74e7.58, 7.49, 4.40, 3.40, 2.38, 1.61 ppm. The 13C NMR spectra of 3,
the aromatic carbon atoms resonated between 168.3 and 111.90 ppm
and aliphatic carbon atoms resonated between 81.80 and 33.26 ppm.
In the MALDI-TOF mass spectrum of bis(1-benzylpiperidin)-4-
oxyphthalocyaninato silicon(IV) 3 the molecular ion peak was
observed at 922.30 [MþH]þ. The UVeVis absorption spectrum of 3
in CHCl3 is shown in SFig.2. The SiPc 3 shows an intense, sharp Q
2.3. Synthesis
2.3.1. 1-benzylpiperidin-4-oxy substituted silicon phthalocyanine
(3)
SiPcCl2 (150 mg, 0.24 mmol), 1-benzylpiperidin-4-ol (158 mg,
0.83 mmol) and sodium hydride (19.92 mg, 0.48 mmol) were mixed
with dry toluene (15 mL) and refluxed for 24 h. The solvent was
then removed under reduced pressure. The product was purified by
column chromatography on aluminum oxide (CHCl3/MeOH 100:2)
to give 3 as a green solid. Yield: 100 mg (34%), m.p. > 300 ꢂC. IR
band at
l
¼ 674 nm in CHCl3, a typically non-aggregated form.
3.2. Aggregation studies
Due to the interaction between their 18
p-electron systems,
(ATR),
1478, 1458, 1450, 1365, 1287, 1255, 1176, 1118, 1084, 1023, 946, 767,
751.1 H NMR (400 MHz, CDCl3), (
): 8.96e8.88 (m, 8H, Pc-Ha),
n
/cmꢀ1: 3062 (AreH), 2946e2884 (Aliph. CeH), 1586, 1512,
phthalocyanines are weak soluble or unsoluble in common organic
solvents because of. In this study aggregation behavior of the SiPc 3
was investigated in different solvents such as 1,4-dioxane, aceto-
nitrile, diethyl ether, dichloromethane, dimethyl formamide,
dimethyl sulfoxide, ethanol, ethyl acetate, hexane, chloroform and
tetrahydrofurane (Fig. 1a). SiPc 3 having Q band in different sol-
vents did not show any aggregation in these solvents suggesting
that the substitution effect of the groups as axial substituent on the
phthalocyanine ring. We also examined concentration effect on the
d
8.44e8.36 (m, 8H, Pc-Hb), 7.74e7.58 (m, 5H, AreH), 7.49 (m, 5H,
AreH), 4.40 (m, 2H, OeCH-), 3.40 (s, 4H, AreCH2eN), 2.38 (m, 8H,
eCH2-), 1.61 (m, 8H, CH2-). 13C NMR (100 MHz, CDCl3), (
d): 168.3,
160.8, 155.8, 145.7, 138.0, 133.5, 130.6, 127.3, 124.6, 122.9, 121.3,
120,8, 117.6, 115.6, 113.3, 118.61, 111.90, 81.80, 54.49, 51.30, 47.62,
33.26. UVeVis (DMF) lmax nm (log ε): 674 (5.12), 644 (4.34), 608
(4.78), 349 (4.58). MALDI-TOF-MS m/z calc. 921.13; found: 922.30
[MþH]þ.
aggregation of SiPc
3
(ranging from 2.0 ꢁ 10ꢀ6 to
12 ꢁ 10ꢀ6 mol dm3) in CHCl3 (Fig. 1b). As shown in Fig. 1b the in-
tensity of absorption bands increases with increasing concentration
and no new bands were observed signifying no aggregation
behavior at these concentrations.
2.4. Electrochemical measurements
All electrochemical measurements were carried out with Gamry
Interface 1000 potentiostat/galvanostat utilizing a three-electrode
configuration at 25 ꢂC. The working electrode was a Pt disc with a
surface area of 0.071 cm2. A Pt wire was served as the counter
electrode and saturated calomel electrode (SCE) was employed as
the reference electrode and separated from the bulk of the solution
by a double bridge. Electrochemical grade tetrabuthylammonium
perchlorate (TBAP) in extra pure dichloromethane (DCM) was
employed as the supporting electrolyte at a concentration of
3.3. Electrochemical studies
Voltammetric analysis of SiPc 3 was performed with CV mea-
surement in dichloromethane (DCM)/tetrabutylammoniumper-
chlorate (TBAP) electrolyte system on a Pt working electrode.
Voltammogram of SiPc 3 was analyzed to derive fundamental
electrochemical parameters including the half-wave peak poten-
tials (E1/2), peak to peak potential separations (
between the first oxidation and reduction processes (D
D
Ep), the difference
0.10 mol dmꢀ3
.
E1/2). The

E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
3
Fig. 1. a) UVeVis spectrum of SiPc 3 in different solvents. b) UVeVis spectrum of SiPc 3 in CHCl3 at different concentrations (25 ꢂC and atmospheric pressure).
results of voltammetric analyses are given in Table 1.
complexes reported in the literature [38], which support the pro-
posed structure of the SiPc synthesized here. Also, HOMO-LUMO
gap of SiPc 3 (
ported in the literature [38]. On the other hand, the peak currents
increased linearly with the square root of the scan rates for scan
rates ranging from 25 to 250 mV sꢀ1 for this SiPc 3 (Fig. 2b).
As shown in Fig. 2a, SiPc 3 shows one irreversible reduction
couple R1 at ꢀ0.85 V (
couple R2 at ꢀ1.54 V (
oxidation couple O1 at 1.07 V (
couples,
Ep values at 0.100 mVsꢀ1 scan rate usually ranged from
D
D
Ep ¼ 288 mV), one reversible reduction
Ep ¼ 95 mV) and one quasi-reversible
Ep ¼ 135 mV). For the reduction
D
E1/2 ¼ 1.92 V) is in compliance with the SiPc re-
D
D
0.060 to 0.120 V, suggesting reversible behavior [37]. Electro-
chemical behavior of SiPc 3 is in agreement with the similar SiPc
3.4. Catalytic studies
The photocatalytic activity of silicon phthalocyanine 3 was
investigated in the oxidation of p-nitrophenol compound in
dichloromethane. The photocatalytic experiments were repeated in
the presence and absence of light and catalyst. It is proved that
presence of the light and catalyst are essential for the oxidation. In
this work, two fragments were determined due to the attack by
catalytically active species. The main product was determined as
hydroquinone and the side product was determined as benzoqui-
none in the oxidation of p-nitrophenol photocatalytic degradation
Table 1
Voltammetric data of the SiPc 3. All voltammetric data were given versus SCE.
Phthalocyanine
Redox processes
aE1/2
bDEp (mV)
cDE1/2
SiPc
R1
R2
O1
ꢀ0.85
ꢀ1.54
1.07
288
95
135
1.92
a
E1/2 values ((Epa þ Epc)/2) were given versus SCE at 0.100 V-1 scan rate.
b
c
D
Ep ¼ Epa-Epc
.
D
E1/2 ¼ E1/2 (first oxidation)- E1/2 (first reduction).

4
E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
Fig. 2. a)CV and SWV of SiPc 3.b) CV of SiPc 3 at various scan rates (ranging from 25 to 250 mV sꢀ1) on a Pt working electrode in DCM/TBAP.
Fig. 3. The oxidation products of p-nitrophenol at room temperature.

E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
5
nitrophenol, Co is the first concentration and C(t) is the concen-
tration of p-nitrophenol as a function of illumination time. This
equation shows a similar profile with the photocatalytic degrada-
tion of the other dyestuffs [40,41]. For this purpose, 100 mL of
0.025 M p-nitrophenol solution and 5 mg of solid catalyst and
oxidant (H2O2) were reacted in a photoreactor for 3 h under visible
light. During the photocatalytic reaction, all samples from taking
reaction medium were diluted with dichloromethane 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 p-nitrophenol has been degraded and after
150 min, the degradation rate has been fixed. Data about photo-
catalytic degradation of p-nitrophenol that was sensitized with
silicone phthalocyanine under visible light were presented in Fig. 4.
Fig. 5 clearly shows that silicon phthalocyanine is good catalyst
for degradation of p-nitrophenol with giving major product (66%)
and side product (22%). Table 2 summarizes all photocatalytic re-
sults with selectivity, TON and TOF values for complex 3. According
to Table 2, silicon phthalocyanine 3 exhibits good catalytic activity
for p-nitrophenol degradation with 1758 TON and 586 TOF values.
To find the optimal reaction conditions, catalyst/substrate ratio was
tested in p-nitrophenol oxidation. When the catalyst/substrate ra-
tio was increased from 0.01/2000 to 1/2000, the rate of the reaction
increased. In contrast, while the catalytic oxidation was processing
from 1/2000 to 50/2000, the conversion fixed to 88%.
Fig. 4. The photocatalytic oxidation of p-nitrophenol with near visible light irradiation
SiPc 3 and in dark. (A mixture of p-nitrophenol compounds (10.85 ꢁ 10ꢀ3 mol), catalyst
(5.43 ꢁ 10ꢀ6 mol, oxidant (2.71 ꢁ 10ꢀ3 mol) and solvent (0.01 L) at 1 h).
In the literature, many reports are available about catalytic ac-
tivities of phthalocyanine (without support) [42e47] but in few
ones visible light was used in catalytic process. Some previously
reported catalysts are summarized in Table 3. Different groups
substituted cobalt(II), iron(II), aluminium(III), copper(II) and metal
free phthalocyanines were investigated on photooxidation of
different pollutants [48e54]. Nyokong and co-workers studied
photocatalytic activities of seven octasubstituted thio and aryloxy
palladium and platinum phthalocyanines in degradation of p-
nitrophenol [55]. According to kinetic studies of this work, there
would be two reaction pathways for degradation of p-nitrophenol
with phthalocyanine catalyst (Fig. 6) [55]. In the another research of
T. Nyokong, singlet oxygen quantum yields and photodegradation
of p-nitrophenol in the presence of zinc tetrasulfophthalocyanine
(ZnPcS4), zinc octacarboxyphthalocyanine (ZnPc(COOH)8) as pho-
tocatalysts are reported [56]. In this work, it is the first time for
investigation of photocatalytic degradation p-nitrophenol with 1-
benzylpiperidin-4-oxy groups substituted SiPc 3 without any oxy-
gen source. The results of photocatalytic experiments are promising
and can be create new researches and micro scale application.
Fig. 5. The conversion of p-nitrophenol, hydroquinone, benzoquinone in photo-
catalytic conditions. (A mixture of p-nitrophenol compounds (10.85 ꢁ 10ꢀ3 mol),
catalyst (5.43 ꢁ 10ꢀ6 mol, oxidant (2.71 ꢁ 10ꢀ3 mol) and solvent (0.01 L) at 1 h and 18
pieces 8W UV lamp).
reaction (Fig. 3).
After the degradation studies, the photodegradation amount of
p-nitrophenol was calculated with the equation below [39]:
.
XðtÞ ¼ Co ꢀ C
Co
ðtÞ
In the equation above, X(t) is the molar fraction of p-
Table 2
Selective oxidation of p-nitrophenol with catalyst 3.
Subs./Ox./Cat
Oxidant
Temperature (oC)
Conversion (%)
SiPc 3
Selectivitya (%)
SiPc 3
TON
TOF (hꢀ1
SiPc 3
)
SiPc 3
2000/500/1
2000/free/1
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
25
25
25
25
25
25
25
25
88
37
e
75
67
e
1758
740
e
586
246
e
2000/500/free
2000/500/1(in dark)
2000/500/0.01
2000/500/0.1
2000/500/10
2000/500/50
9
45
42
39
75
75
180
1.65
23
1758
1758
60
33
46
88
88
0.55
7.67
586
586
All photocatalytic reaction were done in photoreactor with light.
TON ¼ mole of product/mole of catalyst.
TOF ¼ mole of product/mole of catalyst x time.
Conversion was determined by GC.
Reaction Conditions: solvent (dichloromethane), p-nitrophenol (10.85 ꢁ 10ꢀ3 mol), catalyst (5.43 ꢁ 10ꢀ6 mol), oxidant (2.71 ꢁ 10ꢀ3 mol).
a
¼ Selectivity of benzoquinone Reaction time ¼ 3 h.

6
E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
Table 3
Catalytic activities of phthalocyanines towards the photooxidation of different organic compounds in some previously reported catalyst.
Catalyst
Substrate
Rxn Time (h)
Rxn Temp. (oC)
Oxidant
Conv. (%)
Ref.
ZnTsPca
FePcb
Methyl orange-Orange G
Ethyl benzene
Malachite green
2-mercaptoethanol
Süflide ion
10min
9h
30 min
2
1
5
3
nr
rt
nr
rt
rt
27
rt
O2
O2
e
nr
[49]
[50]
[51]
[52]
[53]
[54]
[55]
>99
99.2
nre
CoTNPcc
CoPcd
e
Metal free Pcf
CuPcg
O2
e
70
4-nitrophenol
4-chlorophenol
nrh
CoPcı
O2
99.99
97.05
ZnPcı
ZnTs-CoFerritea ¼ 2-[5-(phenoxy)-isophthalic acid] 9(10), 16(17), 23(24)-tris (tertbutyl) phthalocyaninato Zn (II).
FePc-POFb ¼ four-branched tetra-amine FePc-porous organic framework.
c
CoTNPc/SnIn4S8 ¼ Tetranitrocobalt phthalocyanine/ternary chalcogenide.
CoPcd ¼ Cobaltphthalocyanine/C60
.
Metal free Pcf ¼ Metal free phthalocyanine/TiO2.
CuPcg ¼ Copper phthalocyanine/TiO2.
CoPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato cobalt(II)/TiO2.
ZnPcı ¼ 2,9,16,23-tetrakis-(4-carboxyphenylsulphanyl) phthalocyaninato zinc(II)/TiO2.
nr ¼ not reported.
nre ¼ Turnover number is given as 8.4.
nrh ¼ Quantum yield is given as 1.9.
Fig. 6. Mechanism of p-nitrophenol degradation.
4. Conclusion
Acknowledgement
In conclusion, axially 1-benzylpiperidin-4-oxy units substituted
silicon phthalocyanine 3 was designed and synthesized. SiPc 3 is
highly soluble in most of the organic solvents and are investigated
aggregation behavior in different common organic solvents. The
photocatalytic activity of SiPc 3 was examined for p-nitrophenol
degradation using photochemical reactor. The results indicated that
the catalyst showed good activity for p-nitrophenol degradation to
the corresponding hydroquinone as major product in 1 h at 25 ꢂC.
Cyclic voltammetry was used in order to investigate the electro-
chemical properties of SiPc 3. Electrochemical responses of SiPc 3
support the proposed structure of the complex. Voltammetric
studies suggested that SiPc 3 display reversible/quasireversible/
irreversible redox processes, which are the main requirement for
the technological usage of this compound.
This study was supported by The Research Fund of Kar-
adenizTechnical University, Trabzon, Turkey (Project number:
7687).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molstruc.2019.126994.
References
[1] K.M. Kadish, K.M. Smith, R. Guilard, Handbook of Porphyrin Science, World
Scientific Publishing, Singapore, 2010.
[2] M.P. Donzello, C. Ercolani, V. Novakova, P. Zimcik, P.A. Stuzhin, Coord. Chem.
Rev. 309 (2016) 107e179.
[3] M.P. Donzello, D. Vittori, E. Viola, L.H. Zeng, Y. Cui, K.M. Kadish, J. Porphyr.
Phthalocyanines 19 (2015) 903e919.

E.T. Saka et al. / Journal of Molecular Structure 1199 (2020) 126994
7
[4] M. Kucinska, P. Skupin-Mrugalska, W. Szczolko, L. Sobotta, M. Sciepura,
[29] D.C. Xia, W.C. Li, Synth. Met. 209 (2015) 549e554.
[30] Z. Biyiklioglu, Synth. Met. 162 (2012) 26e34.
[31] Z. Biyiklioglu, Synth. Met. 161 (2011) 508e515.
[32] K. N Kim, C.S. Choi, K.Y. Kay, Tetrahedron Lett. 46 (2005) 6791e6795.
[33] Z. Bıyıklıoglu, H. Alp, Dyes Pigments 132 (2016) 213e222.
[34] G. Cheng, X. Pen, G. Hao, V.O. Kennedy, I.N. Ivano, K. Knappenberger, J. Phys.
Chem. A 107 (2003) 3503e3514.
E. Tykarska, J. Med. Chem. 58 (2015) 2240e2255.
[5] J.T.F. Lau, P.-C. Lo, X.-J. Jiang, Q. Wang, D.K.P. Ng, J. Med. Chem. 57 (2014)
4088e4097.
[6] M.P. Donzello, E. Viola, C. Ercolani, Z. Fu, D. Futur, K.M. Kadish, Inorg. Chem. 51
(2012) 12548e12559.
[7] A. Hagfeldt, G. Boschloo, L.C. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110 (2010)
6595e65663.
[8] M.-E. Ragoussi, M. Ince, T. Torres, Eur. J. Org. Chem. 2013 (2013) 6475e6489.
[9] L. Lochman, J. Svec, J. Roh, K. Kirakci, K. Lang, P. Zimcik, Chem. Eur J. 22 (2016)
2417e2426.
[35] D.D. Perrin, W.L.F. Armarego, Purification of Laboratory Chemicals, second ed.,
Pergamon Press, Oxford, 1989.
[36] J.G. Young, W. Onyebuagu, J. Organomet. Chem. 55 (1990) 2155e2159.
[37] H. Bas¸ , Z. Biyiklioglu, Inorg. Chim. Acta 483 (2018) 79e86.
[38] H. Bas¸ , Z. Biyiklioglu, Organomet. Chem. 791 (2015) 238e243.
[39] A.M. Sevim, J. Organomet. Chem. 832 (2017) 18e26.
[40] I. Altın, M. Sokmen, Z. Bıyıklıoglu, Desalination and Water Treatment 57
(2016) 16196e16207.
[10] V. Novakova, M. Laskova, H. Vavrickova, P. Zimcik, Chem. Eur J. 21 (2015)
14382e14392.
[11] I.V. Nesterova, C.A. Bennett, S.S. Erdem, R.P. Hammer, P.L. Deininger,
S.A. Soper, Analyst 136 (2011) 1103e1105.
[12] P. Zimcik, V. Novakova, K. Kopecky, M. Miletin, R.Z. Uslu Kobak,
E. Svandrlikova, Inorg. Chem. 51 (2012) 4215e4223.
[13] D. Wohrle, G. Schnurpfeil, S.G. Makarov, A. Kazarin, O.N. Suvorova, Macro-
heterocycles 5 (2012) 191e202.
[41] R. Bayrak, C. Albay, M. Koç, I. Altın, I. Degirmenci, M. Sokmen, Process Saf.
Environ. Prot. 102 (2016) 294e302.
[42] A.A. Kamıloglu, I. Acar, Z. Bıyıklıoglu, E.T. Saka, J. Organomet. Chem. 828
(2017) 59e67.
[14] P. Zimcik, A. Malkova, L. Hruba, M. Miletin, V. Novakova, Dyes Pigments 136
(2017) 715e723.
[43] A.A. Kamıloglu, I. Acar, E.T. Saka, Z. Bıyıklıoglu, J. Organomet. Chem. 815e816
(2016) 1e7.
[15] H. Ling, K. Kim, Z. Liu, J. Shi, X. Zhu, J. Huang, Catal. Today 258 (2015) 96e102.
[16] H.R. Rajabi, F. Shahrezaei, M. Farsi, J. Mater. Sci. Mater. Electron. 27 (2016)
9297e9305.
[17] H.R. Rajabi, F. Karimi, H. Kazemdehdashti, L. Kavoshi, J. Photochem. Photobiol.
B Biol. 181 (2018) 98e105.
[44] V. Cakır, E.T. Saka, Z. Bıyıklıoglu, H. Kantelin, Synth. Met. 197 (2014) 233e239.
[45] A.A. Kamıloglu, E.T. Saka, Z. Bıyıklıoglu, I. Acar, H. Kantekin, J. Organomet.
Chem. 745e746 (2013) 18e24.
€
[46] Z. Bıyıklıoglu, E.T. Saka, S. Gokçe, H. Kantekin, J. Mol. Catal. A Chem. 378 (2013)
156e163.
[18] H.R. Rajabi, H. Arjmand, H. Kazemdehdashti, M. Farsi, J. Environ. Chem. Eng. 4
(2016) 2830e2840.
[19] I. Ali, S.R. Kim, S.P. Kim, J.O. Kim, Catal. Today 282 (2017) 1e37, 282.
[20] S.M.S. Chauhan, P. Kumari, S. Agarwa, Synthesis 23 (2007) 3713e3721.
[21] P.-C. Lo, X. Leng, D.K.P. Ng, Hetero-arrays of porphyrins and phthalocyanines,
Coord. Chem. Rev. 251 (2007) 2334e2353.
[47] E.T. Saka, G. Sarkı, H. Kantekin, A. Koca, Synth. Met. 214 (2016) 82e91.
[48] S. Mapukata, N. Kobayashi, M. Kimura, T. Nyokong, J. Photochem. Photobiol. A
Chem. 379 (2019) 112e122.
[49] W.L. He, C.D. Wu, Appl. Catal. B Environ. 234 (2018) 290e295.
[50] M. Lu, B. Li, Y. Zhang, Q. Liang, X. Li, S. Xu, Z. Li, J. Mater. Sci. Mater. Electron. 29
(2018) 16680e16690.
[22] Z. Biyiklioglu, Dyes Pigments 99 (2013) 59e66.
[23] A. Tillo, M. Stolarska, M. Kryjewski, L. Popenda, L. Sobotta, S. Jurga, Dyes
Pigments 127 (2016) 110e115.
[24] Y. Bandera, M.K. Burdette, J.A. Shetzline, R. Jenkins, S.E. Creager, S.H. Foulger,
Dyes Pigments 125 (2016) 72e79.
[51] P. Arunachalam, S. Zhang, T. Abe, M. Komura, T. Iyoda, K. Nagai, Appl. Catal. B
Environ. 193 (2016) 240e247.
[52] V. Iliev, D. Tomova, Catal. Commun. 3 (2002) 287e292.
ꢀ
[53] G. Mele, R. Del Sole, G. Vasapollo, E. García-Lopez, L. Palmisano, M. Schiavello,
J. Catal. 217 (2003) 334e342.
[25] Z. Biyiklioglu, I. Acar, Synth. Met. 162 (2012) 1156e1163.
[26] S. Zongo, M.S. Dhlamini, P.H. Neethling, A. Yao, M. Maaza, B. Sahraoui, Opt.
Mater. 50 (2015) 138e143.
[54] Y. Mahmiani, A.M. Sevim, A. Gül, J. Photochem. Photobiol. A Chem. 321 (2016)
24e32.
[55] T.B. Ogunbayo, E. Antunes, T. Nyokong, J. Mol. Catal. A Chem. 334 (2011)
[27] E.T. Saka, D. Çakır, Z. Biyiklioglu, H. Kantekin, Dyes Pigments 98 (2013)
255e262.
123e129.
[56] E. Marais, R. Klein, E. Antunes, N. Nyokong, J. Mol. Catal. A Chem. 261 (2007)
[28] A.T. Bilgiçli, M. Durdasoglu, E. Kırbaç, M.N. Yarasır, M. Kandaz, Polyhedron 100
(2015) 1e9.
36e42.