Metallophthalocyanines derived with phenyl sulfide by bridging triazole using click chemistry: Synthesis, Computational Study, Redox Chemistry and Catalytic Activity

Article abstract of DOI:10.1016/j.molstruc.2021.130225

Synthesis and characterization of new metallophthalocyanines (M = Zn, Co (II) and Ni (II)) carrying four new triazole units in peripheral positions was presented in this paper. First, 4-(prop-2-yn-1-yloxy)phthalonitrile, 3, was synthesized. Second, azidom

Full text of DOI:10.1016/j.molstruc.2021.130225

Journal of Molecular Structure 1236 (2021) 130225
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Metallophthalocyanines derived with phenyl sulfide by bridging
triazole using click chemistry: Synthesis, Computational Study, Redox
Chemistry and Catalytic Activity
Hüseyin Karacaa,∗, Nagihan Çaylak Delibas¸ b, Serap Sag˘lama, Hasan Pis¸ kinc, Serdar Sezerd,
Tuncer Hökeleke, Murat Teker a
a Department of Chemistry, Sakarya University, 54187 Sakarya, Turkey
b Department of Physics, Sakarya University, 54187, Esentepe, Sakarya, Turkey
c
˙
Bog˘aziçi University, Department of Physics, 34342, Bebek, Istanbul, Turkey
d Department of Pharmacology, Faculty of Medicine, Suleyman Demirel University, Isparta, Turkey
e Department of Physics, Hacettepe University, 06800 Beytepe-Ankara, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Synthesis and characterization of new metallophthalocyanines (M
=
Zn, Co (II) and Ni (II)) carry-
Received 23 August 2020
Revised 3 February 2021
Accepted 26 February 2021
Available online 23 March 2021
ing four new triazole units in peripheral positions was presented in this paper. First, 4-(prop-2-yn-1-
yloxy)phthalonitrile, 3, was synthesized. Second, azidomethyl phenyl sulfide, 4, was added to this struc-
ture in order to obtain a triazole unit catalyzed by sodium ascorbate and CuSO4.5H2O in DMSO. Common
spectroscopic methods such as FT-IR, 1H-NMR, 13 C-NMR, HRMS and UV-Vis spectroscopy techniques was
used for characterization of synthesized structures. The molecular structure of the phthalonitrile com-
pound 5 was confirmed by single-crystal X-ray diffraction experiment. Morover, by using HF and B3LYP
method and 6–31++g(d,p) basis set, 1H and 13 C NMR chemical shifts, IR and UV–vis spectrums were
theoretically calculated in gas phase for the optimized structure of 5. The obtained FTIR spectra and
NMR spectra showed that the desired molecules were synthesized, and mass spectra confirmed these
molecules. Electronic absorption spectra have shown that phthalocyanines are non-aggregable molecules.
The cyclic voltammetry data of the phthalocyanines has shown that the Pc-6 has two reduction reac-
tions and two oxidation reactions while the Pc-7 and Pc-8 have one reduction reaction and one oxida-
tion reaction. Furthermore, the cobalt(II)phthalocyanine, Pc-7, was investigated as oxidation catalyst for
the catalytic oxidation of 2-mercaptoethanol. Turnover number, initial reaction rate and the oxygen con-
sumption values were found in the catalytic oxidation of 2-mercaptoethanol as 18.09, 0.12 μmol.s−1 and
6.88 μmol.min−1, respectively.
Keywords:
Phthalocyanine
triazole
computational
redox
catalysis
click
© 2021 Elsevier B.V. All rights reserved.
1. Introduction
medical applications [32-43], fuel cell applications [44-54], elec-
trocatalysis [55-66], photovoltaic cell elements in energy produc-
Phthalocyanine is one of the tetraizoindole derivative, which is
one of the main topics of interest in both basic science and ap-
plied studies last three decades. Over the years, it has become the
subject of more research [1-8]. Derivatization of phthalocyanines
with various functional groups, either peripheral or non-peripheral,
yields unique properties. Studies on the potential uses of these
unique properties of phthalocyanines on the remarkable areas such
as dyes and catalysts [9-13], sensitive elements in chemical sen-
sors [14-18], organic photovoltaic devices [19-24], electrochromic
display devices [25-31], photodynamic therapy of cancer and other
tion [67-81], molecular metals and conductive polymers [82-87]. It
is important not only to improve the derivatization properties of
phthalocyanines, but also to make them usable. Because only the
phthalocyanine macro ring is not soluble. Derivation is essential to
be soluble in both water and organic solvents [88-90].
Recently, triazoles have received increasing attention as an im-
portant class of heterocyclic compounds in medicinal chemistry
and other chemistry applications [91-98]. In chemical synthesis,
“click” chemistry is a class of biocompatible small molecule reac-
tions that are commonly used in bioconjugation, which allow com-
bining preferred substrates with specific biomolecules. It is also
seen that click chemistry has begun to be applied in phthalocya-
nines [99-101]. It was thought that the triazole unit would add IR
∗
Corresponding author.
E-mail address: karaca@sakarya.edu.tr (H. Karaca).
https://doi.org/10.1016/j.molstruc.2021.130225
0022-2860/© 2021 Elsevier B.V. All rights reserved.

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
property close to phthalocyanine. The absorbance of the obtained
zinc phthalocyanine at 708 nm in the UV-visible spectrum sup-
ported this idea.
started simultaneously and then time dependent oxygen consump-
tion was calculated. The characterization of the catalytic activity of
Co(II)phthalocyanine Pc-7 was set by turnover number, TON (con-
version mol oxygen per mol phthalocyanine), initial reaction rate
(μmol oxygen consumption per second) and the oxygen consump-
tion (μmol/min) [102-105].
In this study, 4-((3-((phenylthio)methyl)-3H-1,2,4-triazol-5-
yl)methoxy)phthalonitrile, 5, as monomer and metallophthalo-
cyanines were synthesized. The molecular structure of compound
5 was confirmed by the single crystal X-ray diffraction (XRD)
method. The possible intermolecular interactions present within
the single crystal of 5 have been revealed by the analysis of
XRD data. Furthermore, the structural and spectral properties of
compounds 5 was computationally determined. We have investi-
gated redox chemistry of triazole bridged phenyl sulfide-derived
metallophthalocyanines. The catalytic activity of Co (II) phthalo-
cyanine was investigated. This is based on the oxidation reaction
of 2-mercaptoethanol with dissolved oxygen. The novel designed
and synthesized metallophthalocyanines having triazole bridged
phenyl sulfide on the periphery were characterized by 1H-NMR,
13C-NMR, IR, MALDI-TOF, and UV/Vis spectra and then reported.
The calculation of the turnover number is made by dividing
moles of oxygen by moles of phthalocyanine. The initial rate of the
reaction is calculated by setting the first order derivative of the re-
action rate equation to zero. The oxygen consumption is calculated
by dividing moles of oxygen by time.
2.4. Synthesis
2.4.1. 4-(prop-2-yn-1-yloxy)phthalonitrile, 3
1.00
g (5.78 mmol) 4-nitrophthalonitril and 6.00 g (43.46
mmol) K2CO3 were stirred in 12 mL DMSO in a half hour. Then
0,32 g (5.78 mmol) propargyl alcohol was added and continued
stirring for next three hours under the argon atmosphere at room
temperature. 100 mL water was poured into the reaction vessel,
then the crude product was extracted with DCM. The eluent con-
taining the product was dried over MgSO4, then the solvent was
dried on a rotary evaporator under vacuum. The obtained prod-
uct to afford 3 as solid was cleaned by column chromatography
on silica gel by using the ethyl acetate/hexane as eluent. Green
solid (53,70 mg, 81% chemical yield). Melting point: 108 °C. FT-
IR (ATR System, cm−1): 3287, 3119, 3077, 2230, 2135, 1596, 1494,
1321, 1260. 1H NMR (300 MHz, CDCl3) δ: δ 8.09 (d, J = 8.8 Hz, 1H),
7.80 (d, J = 2.5 Hz, 1H), 7.49 (dd, J = 8.8, 2.7 Hz, 1H), 5.00 (s, 2H),
3.71 (d, J = 1.6 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ: 160.5, 135.2,
120.2, 119.9, 117.4, 115.5, 115.2, 108.2, 77.8, 76.2, 56.6. Anal. Calc.
for C, 72.52; H, 3.32; N, 15.38 %. Found: C:72,02; H:3,42; N:15,48 %.
HRMS: m/z [M] calcd.182.18 For C13H11 NO: found [M+H]+ 199.15.
2. Experimental
2.1. General
The glassware was heated in an oven at 150°C for 1 hour and
then cooled under a nitrogen atmosphere and used in the experi-
ments. The reaction solvents were distilled off with the indicated
drying agents: DMAE (CaH2), DMF (CaH2). All chemicals were pur-
chased from commercial suppliers and used directly. Barnstead
Electrothermal 9200 model melting point device were used to de-
termine melting points of synthesized molecules. Merck Silica Gel
60 was used for flash column chromatography in a thick-walled
glass column. Thin layer chromatography (TLC) was used to en-
able monitoring of the reaction through by using the silica gel
precoated aluminum sheet (Merck Silica Gel PF-254). Polymolyb-
denum phosphoric acid solution in ethanol and UV light were used
to visualize stains on the TLC plate. Solvents was evaporated under
vacuum by using a rotary evaporator after the All extracts were
dried over anhydrous magnesium sulfate.
2.4.2. 4-((3-((phenylthio)methyl)-3H-1,2,4-triazol-5-
yl)methoxy)phthalonitrile, 5
0.86 g (4.70 mmol) 3 and 0.70 g (4.70 mmol) azidomethyl
phenyl sulfide 4 were dissolved in 18 mL DMSO in a round-bottom
flask and stirred under the nitrogen atmosphere for half an hour.
Then 0.13 g (0.47 mmol) sodium ascorbate and 0.12 g (0.47 mmol)
CuSO4.5H2O were added together into the flask and continued stir-
ring for 24 hours at room temperature under the nitrogen atmo-
sphere. 200 mL water was added into the reaction mixture. The
white precipitate was extracted with DCM. The DCM containing
the product was dried over MgSO4, then the solvent was dried
on a rotary evaporator under vacuum. The obtained was cleaned
by column chromatography on silica gel by using the ethyl ac-
etate/hexane as eluent. The white solid (1.47 g, 89.96 % chemi-
cal yield). Melting point: between 180, 190 °C. FT-IR (ATR Sys-
tem, cm−1): 3185, 3125, 3085, 2991, 2941, 2230, 1592, 1500, 1471,
1318, 1252, 1224, 1058, 987, 852, 809, 746, 690, 521, 490. 1H NMR
(300 MHz, CDCl3) δ 7.71 (d, J = 8.3 Hz, 1H), 7.60 (s, 1H), 7.33 (d,
J = 2.4 Hz, 1H), 7.24 (s, 3H), 7.21–7.18 (m, 3H), 5.59 (s, 2H), 5.22 (s,
2H). 13C NMR (75 MHz, DMSO-d6) δ 161.30, 135.53, 132.27, 131.68,
129.81, 129.10, 123.12, 123.09, 120.51, 119.72, 117.67, 115.76, 115.34,
108.10, 62.69, 54.28. Anal. Calc. For C:62,23; H:3,77; N:20,16; S:9,23
%. Found: C,61.82; H,3.65; N:20,36; S:9,32 %. HRMS: m/z [M] calcd.
347.40 For C21H13N3O; found [M+H]+ 348.25.
2.2. Spectroscopy
1H NMR and 13C NMR spectra were recorded in CDCl3 and
DMSO- d6 using a VARIAN Infinity Plus 300 MHz NMR spectrome-
ter. The ppm was used to express chemical shifts relative to CDCl3
(δ7.26 and 77.0 for 1H and 13C NMR, respectively) and TMS as the
internal standard. FT-IR spectra were recorded on a Perkin Elmer
Spectrum Two FT-IR spectrometer. HRMS and MALDI-TOF spectra
were recorded on an Agilent Technologies 6530 Accurate-Mass Q-
TOF LC/MS device. UV-visible spectrums were recorded on a Shi-
madzu UV 2600 model Spectrophotometer.
2.3. Catalytic oxidation of 2-mercaptoethanol
CyberScan DO 300 oxygen meter was used to measure the
dissolved oxygen in reaction mixture in the closed system.
Co(II)phthalocyanine (Co(II)Pc) (Pc-7) was dissolved as 0.380 μmoL
in 50 mL THF. The reaction vessel was bubbled with air bub-
bles to saturate the solution to oxygen. We have used air oxy-
gen for this oxidation. Then 2.07 mmol 2-mercaptoethanol was
added. A 5500:1 ratio of 2-mercaptoethanol and Co (II) phthalo-
cyanine, which is a good ratio of catalytic activity, was used. Af-
ter adding the 2-mercaptoethanol, 1 mL of 0.25 wt% aqueous
sodium hydroxide solution was poured into the reaction vessel
and system was closed. Measurement of the dissolved oxygen re-
maining in the reaction mixture from the oxidation reaction was
2.4.3. General procedure for the synthesis of phthalocyanines, Pc-6,
Pc-7 and Pc-8
Metal salts, Zn(OAc)2.2H2O, Co(Oac)2.4H2O and NiCI2.2H2O,
were taken at 1/4 ratio relative to the phthalonitrile, 5, to syn-
thesize the metallophthalocyanines. Phthalonitrile, 5, was dissolved
in a mixture of DMEA/DMF (1:2). The mixture was stirred for half
2

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Table 1
an hour, metal salt was added to the mixture and continued stir-
ring at 150 °C for 24 hours under the nitrogen atmosphere. Reac-
tion 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.
Crystallographic information, data collection and refinement parameters for
monomer phthalonitrile 5.
CCDC Number
2021080
18H13N5OS
Empirical formula
Formula weight (g/mol)
Temperature (K)
C
347.39
100
˚
Wavelength (A)
Mo Kα radiation (0.71073)
2.4.4. Zinc phthalocyanine, Pc-6
Crystal system
Space group
Monoclinic
Dark green solid, mp >300 °C, (147 mg, 40.1 % chemical yield).
FT-IR (ATR System, cm−1): 3054, 2919, 2851, 1608, 1474, 1411, 1343,
1224, 1046, 815, 746, 690, 456. 1H NMR (300 MHz, DMSO-d6) δ
8.54–8.36 (m, 8H), 7.93–7.79 (m, 8H), 7.53–7.39 (m, 8H), 7.38–7.21
(m, 12H), 6.13–5.97 (m, 8H), 5.79–5.68 (m, 8H). Anal. Calc. for C,
59.44; H, 3.60; N, 19.25; O, 4.40; S, 8.81; Zn, 4.49 %. Found: C,
59.32; H, 3.69; N, 19.19 %. MALDI-TOF MS: m/z [M]+ calcd. For
C72H52N20O4S4Zn: 1454.96; found [M+Na]+ 1477.65.
Pc
˚
a (A)
11.7491 (6)
˚
b (A)
5.4135 (3)
˚
c (A)
26.1548 (13)
α (°)
β (°)
γ (°)
90.0
99.719 (3)
90.0
3
˚
Volume (A )
1639.67 (15)
Z
4
Crystal size (mm)
Crystal description
Calculated density (g cm−3
0.18 × 0.12 × 0.09
2.4.5. Cobalt (II) phthalocyanine, Pc-7
Block, colourless
)
1.407
Dark green solid, mp >300 °C, (75mg, 30.8 % chemical yield).
FT-IR (ATR System, cm−1): 3138, 3057, 2919, 2851, 1602, 1477, 1408,
1327, 1277, 1227, 1096, 1046, 821, 743, 690, 487. Anal. Calc. For C,
59.70; H, 3.62; N, 19.34; O, 4.42; S, 8.85; Co, 4.07 %. Found: C,
59.64; H, 3.75; N, 19.21; S, 8.73 %. MALDI-TOF MS: m/z [M]+ calcd.
For C72H52N20O4S4Co: 1448.52; found [M+4H]+: 1452.36.
Absorption coefficient μ (mm−1
)
0.21
F (000)
720
θ range for data collection (°)
h, k, l
2.6° to 27.5°
−15/15, -7/7, -34/34
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit on F2
25761
7481
7205 / 2 / 452
1.08
2.4.6. Nickel (II) phthalocyanine, Pc-8
Final R indices (Data; I > 2σ[I])
R1 = 0.0663, wR2 = 0.1613
0.56 and -0.79 with 0.042 R.M.S.
Dark green solid, mp >300 °C, (130 mg, 53.5 % chemical yield).
FT-IR (ATR System, cm−1): 2922, 2854, 1605, 1471, 1346, 1230,
1093, 1043, 812, 743, 690. 1H NMR (300 MHz, DMSO-d6) δ 8.34–
8.06 (m, 8H), 7.51–7.09 (m, 28H), 6.05–5.78 (m, 8H), 5.35–5.17 (m,
8H). Anal. Calc. For C72H52N20O4S4Ni C, 59.71; H, 3.62; N, 19.34;
Ni, 4.05; O, 4.42; S, 8.85 %. Found: C, 59.62; H, 3.68; N, 19.25;
S 8.74 %. MALDI-TOF MS: m/z [M]+ calcd. For C72H52N20O4S4Ni:
1448.28; found [M+K]+: 1452.28.
3
˚
Largest diff. Peak and hole (e A- )
2.6. Quantum chemical calculation method
Quantum chemical calculations are realized in order to ob-
tain HOMO, LUMO, E, chemical hardness, global softness, elec-
tronegativity, nucleophilicity and chemical potential. A calculation
of monomer phthalonitrile 5 was performed by using Gaussian
16W [113] and the resulted structure was visualized with the
help of GausView 6.0.16 [114]. The quantum chemical calculations
of monomer phthalonitrile 5 in gas phase were obtained by us-
ing of Hartree Fock and Becke-3-Parameter-Lee-Yang-Parr (B3LYP)
[115] methods with 6-311++G(d,p) basis set.
2.5. X-ray data collection and refinement for the compound 5
Bruker APEX II Quazar three circle diffractometer with mono-
˚
chromated Mo-K radiation (λ=0.71073 A) was used to collect
α
the HKL data of the solid-stated single crystal of 5. For the ex-
periment, a block-like colourless crystal was taken by dimensions
of 0.18 × 0.12 × 0.09 (mm). Totally, 25761 reflections were ob-
served, 7481 reflections were independent, and 7205 reflections
were greater than 2σ(F2). The crystal structure was solved by us-
ing the direct methods in SHELXS and refined by the least-squares
(F2) method provided by SHELXL in Olex2 software. Firstly, all of
the atoms (except hydrogens) were placed correctly as isotropic.
Then, refined as anisotropic. All the hydrogen atoms were placed
geometrically, and the complete structure was refined a few times
to get best fit. For the resulted “cif” file, a twinning was observed
with the FCF based twin law (0 0 1) [2 0 5] (BASF 0.14). Therefore,
a new HKLF 5 file was generated by using “TwinRotMat” function
given in PLATON software and the resulted structure was refined a
few more times. Finally, the goodness of fit (S) has been obtained
as 1.08. Table 1 presents the summary of crystallographic informa-
tion, data collection and the refinement parameters. In addition,
the solid-stated crystal stabilization dynamics have been analysed
by the PLATON program [106]. The check cif validation done at
the check-CIF/PLATON web-based IUCr service [107]. The crystallo-
graphic information file (cif) has been uploaded to the data centre
with CCDC number 2021080.
3. Results and discussion
3.1. Synthesis
It is known from the literature that the binding of bulky sub-
stituents to phthalocyanines, either peripheral or non-peripheral
positions, prevents aggregation, thereby increases the solubility of
phthalocyanines in organic solvents and in aqueous media. In ad-
dition, the metal exchange at the center of the phthalocyanine af-
fects the solubility of the phthalocyanines [1,2,88,89]. It was syn-
thesized a triazole bridged phenyl sulfide at peripheral positions as
phthalocyanine derivatizer. Thus, since a bulky group was formed,
its solubility was expected to be high and so was it. The syn-
thesis was started by the reaction of propargyl alcohol with 4-
nitrophthalonitrile in the presence of potassium carbonate under
nitrogen atmosphere and at room temperature. After the column
chromatography isolation chemical yield was 81% and thus the
compound 3 has been obtained via the SNAr type substitution re-
action between propargyl alcohol 2 and 4-nitrophthalonitrile 1. A
triazole bridged phenyl sulfide-derived phthalonitrile 5 was syn-
thesized by the catalytic reaction of compound 3 and azidomethyl
phenyl sulfide with CuSO4 and sodium ascorbate in DMSO at room
temperature. The chemical yield was 89.96 % (Scheme 1(a)). We
have previously published phthalocyanines having triazole func-
tionality [99]. Moreover, these triazole bridged phenyl sulfide-
Data collection: Bruker Instrument Service [108]; data in-
tegration and reduction: SAINT V8.34A [109]; absorption cor-
rection: multi-scan method implemented in SADABS [110]; pro-
gram(s) used to solve structure: SHELXS; program(s) used to re-
fine structure: SHELXL [111]; molecular graphics and software
used to prepare material for publication: Olex2 [112].
3

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Scheme 1. (a) Synthesis of phthalonitrile 3, 5 and target phthalocyanine skeleton (b) Synthesis of target phthalocyanines Pc-6, Pc-7 and Pc-8.
derived metallophthalocyanines are newly synthesized and inves-
tigated. This derivatization will provide phthalocyanines with new
properties and application opportunities. In this study, the redox
behavior of phthalocyanines together with the crystal structure of
the 5 compounds were investigated. Such derivatization of Metallo
Pc’s will allow for increased solubility and biological activity [116].
We have reported the redox chemistry of these novel phthalocya-
nines.
Pc-6 and Pc-8 were received in DMSO. Moreover, elemental analy-
sis and HRMS and MALDI-TOF measurements of synthesized com-
pounds were taken. Thus, the structures of the synthesized MPCs
were elucidated by 1H NMR technique. These structures were con-
firmed by FTIR spectra and molecular mass analysis.
3.2. Structure Elucidation
The structures of compounds 3 and 5 are qualified by 1H
and 13C NMR spectra and approved by FT-IR spectra. The synthe-
sized phthalonitrile 5 was used as initial monomer for synthe-
sis of metallophthalocyanines Pc-6, Pc-7 and Pc-8. Zn(OAc)2.2H2O,
NiCI2.2H2O and Co(OAc)2.4H2O salts have been used in cyclote-
tramerization of 5, using DMEA as the catalyst at high tempera-
ture in DMF. An isomeric mixture of the desired metallo Pcs were
synthesized as expected (Scheme 1 (b)). The 1H NMR spectra of
The FTIR spectra clearly shows that the desired compounds are
synthesized successfully at each step of the synthesis. Fig. 1 shows
calculated and experimental FTIR spectra. The band viewed at 1592
cm−1 in compound 5 can be attributed to C=C double bond. This
band shifts to 1608 cm−1 in Pc-6¸ 1602 cm−1 in Pc-7 and 1605
cm−1 in Pc-8 because of extra aromatic rings and extra aromati-
zation. The bands viewed at 2231 cm−1 in compound 3 and 2230
cm−1 in compound 5 can be attributed to C N triple nitrile bond
≡
4

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Fig. 1. The calculated (a) HF, (b) B3LYP and (c) experimental FTIR spectra.
stretching vibrations. Cyclotetramerization of monomer 5 and for-
mation of phthalocyanines clearly show that this band at which is
2230 cm−1 in the FTIR spectrum disappears. Other groups below
2000 cm-1 do not have disturbing changes. The bands that is at-
tributable to phthalocyanine skeletal vibrations [28,51] are seen at
3054, 2919, 2851, 1608, 1474, 1411, 1343, 1224, 1046, 815, 746, 690,
456 cm−1 are observed for Pc-6. The phthalocyanines Pc-7 and Pc-
8 show very similar peaks 3138-487 cm−1 in Fig. 2.
compound 5 have four aliphatic protons as two CH2 group. Both
of the CH2 groups have singlet proton NMR as expected, one is at
5.59 ppm and second is at 5.22 ppm. Fig. 3 shows calculated in HF
and B3LYP and experimental NMR spectrums. The 1H-NMR spec-
tra of phthalocyanine of Pc-6, shows the peaks in aromatic region
with small differences in chemical shifts. The peak of CH2 groups
are seen between 6.13-5.97 ppm for 8H and 5.79-5.68 ppm for 8H.
These peaks of CH2 groups Pc-8 are seen between 6.05-5.78 for 8H
and 5.35-5.17 ppm for 8H. These results are consistent. Since the
paramagnetic nature of cobalt inhibited NMR recording, the 1H-
NMR spectrum of cobalt phthalocyanine, Pc-7, was not recorded.
The mass spectra of phthalocyanines, Pc-6, Pc-7 and Pc-
8, were also taken and shown in Fig. 4. Molecular ion peaks
are identified 1477.65 as the [M+Na]+ for Pc-6, 1452.36 as the
The compounds 3 and 5 have mostly aromatic structure so most
of the proton peaks are between 8-6 ppm. The compound 3 has
an acetylenic hydrogen having a doublet peak at 3.71 ppm with
J=1.6 Hz. This peak disappeared on the next step because of oc-
curring the triazole unit by using acetylene. The compound 3 also
have a second peak at 5.00 ppm under the aromatic region. The
5

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Table 2
Hydrogen-bond geometry.
˚
˚
˚
D—H•••A
D—H (A)
H•••A (A)
D•••A (A)
D—H•••A (°)
C10’—H10’A•••N3’i
C10’—H10’B•••N5ii
C16—H16•••S1’iii
C8’—H8’•••N2’i
C10—H10A•••N3iv
C10—H10B•••N5’v
C8—H8•••N2iv
0.99
0.99
0.95
0.95
0.99
0.99
0.95
0.99
0.99
2.48
2.51
2.85
2.44
2.52
2.51
2.34
2.59
2.58
3.461
3.415
3.698
3.242
3.490
3.452
3.206
3.394
3.491
170
151
150
142
166
158
151
139
153
C7—H7B•••N3’iii
C7’—H7’B•••N3vi
Symmetry codes: (i) x, y+1, z; (ii) x+1, −y, z−1/2; (iii) x−1, y+1, z;
(iv) x, y−1, z; (v) x, −y+2, z+1/2; (vi) x+1, y−1, z.
As can be clearly seen from the inset graphics in Fig. 5 that all
of the phthalocyanines, Pc-6, Pc-7 and Pc-8, show non-aggregation
behaviour in the concentration range 10−5 and 10−4 M. That is
to say, they all have very good solubility in chloroform, which is
an organic solvent. All of three Pcs are able to use for appropriate
applications. So, the application studies should be performed with
these phthalocyanines.
3.4. Results of X-ray diffraction experiment of compound 5,
(C18 H13 N5OS)
A monoclinic (Pc) single crystal of the compound 5 has formed
˚
˚
with the unitcell parameters of a = 11.7491 A, b = 5.4135 A,
˚
c = 26.1548 A, and β = 99.719°. While four molecules are form-
ing the unit-cell, two of them have created the asymmetric unit
unit. Fig. 6 presents the atomic arrangement for the asymmetric
unit with the atomic labels and the gravity centres (Cg). For clar-
ity, the hydrogen atom labels were not provided in the figure. But
the hydrogen atoms have been labelled as the same numbers as
the carbon atoms to which they are bounded (like C4—H4).
Fig. 2. FTIR spectra of compounds 5, Pc-6, Pc-7 and Pc-8.
Molecule Description: The asymmetric unit contains no H•••H
intra-molecular interaction within the possible Van der Waals
ranges. For the asymmetric unit, there are six rings observed as
shown in the Fig. 6 (a). Two of them were five-membered rings
and rest of them six-membered rings. Here the five membered
rings A (N1-N2-N3-C9-C8) and A’ (N1’-N2’-N3’-C9’-C8’), and the
six membered rings B (C1—C6), B’ (C1’—C6’), C (C11—C16), and
C’(C11’—C16’) exhibited perfect mean planes with the RMS val-
[M+4H]+for Pc-7 and 1487.28 as the [M+K]+. In the mass spec-
tra of phthalocyanines the presence of the molecular ion peaks at
m/z = 1477.65 [M+Na]+, 1452.36 [M+4H]+ and 1487.28 [M+K]+
respectively, clearly indicates the formation of the designed struc-
tures in Scheme 1.
˚
˚
˚
˚
˚
ues of 0.00186 A, 0.00126 A, 0.0037 A, 0.0102 A, 0.0088 A, and
˚
3.3. UV-Vis absorption spectra
0.0037 A, respectively. For the molecule 1 of asymmetric unit, a
68.34° dihedral angle has been observed between the rings A and
B, while it was 66.83° between the A and C. The phenyl and tri-
azole groups bonded together via S1 atom with a bond angle of
100.11° (C1—S1—C7). Where the bond lengths are C1—S1= 1.79
The UV-Visible spectra of Pc-6, Pc-7 and Pc-8 was recorded by
using chloroform as solvent over a wide range concentration be-
tween 10−5 and 10−4 M. The electronic absorption spectra of ph-
thalocyanines can be seen in Fig. 5 (a), (b) and (c) for Pc-6, Pc-
7 and Pc-8 respectively in the range of 300-800 nm. The typical
Soret bands around 350 nm are see for all of the MPc’s in Fig. 5.
The non-aggregation behavior of phthalocyanines is seen from the
figures. The electronic absorption spectra figures show typical non-
aggregated phthalocyanines. But, aggregation may occur as high
concentrations are reached. This is also evident in electrochemical
measurements. The insets in Fig. 5 which are seen as an almost
linear lines, gave linear regression coefficients of 0.9819, 0.961 and
0.9957 for phthalocyanines Pc-6, Pc-7 and Pc-8. Fig. 5 (a) shows
that Pc-6 has a strong Q band at 708 nm in chloroform having
a shoulder at 648 nm with a vibronic band at 624 nm and also
a Soret band peaking at 360 nm. The Fig. 5 (b) shows that Pc-7
has also a Q band at 680 nm in chloroform having a shoulder at
616 and also a Soret band peaking at 332 nm. On the other side
Fig. 5 (c) shows that Pc-8 has a Q band at 616 nm with a shoulder
at 672 nm and also has a Soret band peaking at 332 nm.
˚
˚
A and S1—C9= 1.80 A. Besides, the phthalonitrile is bonded to
triazole group via O1 atom with a bond angle of 117.97° (C10—
˚
O1—C11), where the bond lengths are C10—O1= 1.45 A and O1—
˚
C11=1.35 A. The molecule 2 exhibited slightly different geometric
properties than molecule 1 such as the dihedral angle between the
rings A’ and B’ is 60.22 °, and between the rings A’ and C’ is 68.95°.
Furthermore, very similar bond angles of 101.10° (C1’—S1’—C7’) and
117.52° (C10’—O1’—C11’) have been observed with the similar bond
˚
˚
˚
lengths of C1’—S1’=1.78 A, S1’—C7’= 1.80 A, C10’—O1’= 1.44 A, and
˚
O1’—C11’=1.36 A.
Supramolecular Dynamics: Fig. 6 (b) presents the monoclinic
molecular assembly of compound 5 with the unitcell through the
(010) view. Here the solid-stated crystal structure has been stabi-
lized by the domination of D—H•••A, Cg•••Cg and Y—X•••Cg inter-
molecular interactions. All these possible interactions have been
listed in the Table 2, Table 3, and Table 4, respectively. In addi-
tion to the hydrogen bonds (D—H•••A), the Cg•••Cg interactions be-
6

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Fig. 3. (a) HF, (b) B3LYP and (c) experimental calculated NMR spectrums of compund 5.
tween six-membered rings have contributed to stabilize the crystal
structure along b-axis while the Cg•••Cg interactions between five-
membered rings have contributed to stabilization along a-c plane.
In order to visualize the intermolecular interactions and quan-
tify the percentages of interactions present in the crystal structure
of compound 5, the Hirshfeld surface analysis of the asymmetric
unit has been done by using the “Crystalexplorer17” software [117].
Fig. 7 (a) presents the Hirshfeld surfaces in two different views
with the “dnorm”, “shape index” and “curvedness” modes. The
red zones on the dnorm show where the strongest intermolecu-
lar interactions are. Besides, the coloured surfaces provided by the
shape index is mapping the Cg•••Cg interactions via the adjacent
7

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Table 3
The inter-molecular π•••π (Cg•••Cg) interactions.a
b
c
d
e
No
Cg(I) •••Cg(J)
Symmetry
Cg•••Cg
Cg(I)-perp
Cg(J)-perp
α
1
Cg(1)•••Cg(2)
Cg(1)•••Cg(1’)
Cg(1)•••Cg(1’)
Cg(1)•••Cg(2’)
Cg(1)•••Cg(2’)
Cg(2)•••Cg(2)
Cg(2)•••Cg(2’)
Cg(2)•••Cg(3’)
Cg(3)•••Cg(1)
Cg(3)•••Cg(3)
Cg(3)•••Cg(2’)
Cg(1’)•••Cg(2)
Cg(1’)•••Cg(2)
Cg(1’)•••Cg(2’)
Cg(2’)•••Cg(2)
Cg(2’)•••Cg(2’)
Cg(2’)•••Cg(3’)
Cg(3’)•••Cg(3’)
x, y, z
4.628
5.014
4.068
5.935
5.361
5.413
5.140
4.131
5.918
5.413
5.958
5.368
5.657
4.787
5.244
5.414
5.151
5.413
3.542
3.898
3.004
1.224
1.769
2.765
1.394
3.415
2.388
3.257
0.031
0.898
1.867
3.569
1.785
2.991
3.399
3.276
3.852
3.049
3.508(3)
4.851
4.393
2.765
4.550
3.592
3.793
3.258
4.633
4.912
4.018
3.700
4.385
2.991
3.777
3.276
68.3
14.4
14.4
68.4
68.4
0.0
2
x-1, y, z
x-1, y+1, z
x, y, z
3
4
5
x, y+1, z
x, y-1, z
x, y+1, z
x, y, z
6
7
64.6
13.1
66.8
0.0
8
9
x, y-1, z
x, y-1, z
x-1, y, z
x, y-1, z
x, y, z
10
11
12
13
14
15
16
17
18
87.8
76.5
76.5
60.2
64.6
0.0
x, y, z
x, y, z
x, y-1, z
x, y-1, z+1/2
x, y-1, z
6.3
0.0
a
b
c
˚
Cg•••Cg < 6.0 A. Distances between centroids of the rings. Perpendicular distance of
d
e
˚
˚
Cg(I) on ring J plane (A). Perpendicular distance of Cg(J) on ring I plane (A). Dihedral angle
between planes I and J (°).
Table 4
Inter-molecular Y—X•••Cg interactions.a
b
c
d
e
Y—X•••Cg(I)
Symmetry
X•••Cg(I)
X-perp
Y—X•••Cg
Y•••Cg
C17—N4•••Cg(3)
C17’—N4’•••Cg(3’)
C18’—N5’•••Cg(2’)
x, y-1, z
3.609
3.532
3.556
3.431
3.397
3.419
89.6
91.5
85.0
3.777
3.741
3.637
x, y+1, z
x, y-1, z+1/2
a
b
c
˚
Cg•••Cg < 4.0 A. Distance from X atom to Cg (I) . Perpendicular distance from X atom
to ring plane. Angle between Y—X•••Cg(I) (°).e Distance from Y atom to Cg(I). All distances
d
˚
have been represented as in the unit of A.
Table 5
blue and red triangles. Curvedness image visualize the relatively
flat surfaces.
The quantum chemical parameters of compound 5 cal-
culated with HF and B3LYP 6.311+G(d,) (eV).4.
The 2D fingerprint plots given in Fig. 7 (b) indicate that the
N•••H / H•••N (37.3 %) contact (C—H•••N) is the major contributor
for the Hirshfeld surface while the H•••H (19.3 %), C•••H / H•••C
(17.5%), C•••N / N•••C (5.7%, C—N•••Cg), S•••H / H•••S (4.9%), and
O•••H / H•••O (4.1%) contacts are making less significant contribu-
tions. Because of the π••• π interactions in the crystal structure,
there is a contribution of C•••C (3.8%). And the other contacts are
making very small contributions such as S•••N / N•••S (2.3%), N•••N
(2.0%), C•••S / S•••C (1.8%), C•••O / O•••C (1.1%), and O•••S / S•••O
(0.2%).
Compound 5
HF
B3LYP
EHOMO
-9,73134
0,71539
10,44673
0,19145
1,94528
9,73134
-0,71539
5,22336
4,50798
-7,16585
-2,39215
4,77370
0,41896
4,78431
7,16585
2,39215
2,38685
4,77900
ELUMO
Band Gap,
E
Global softness, σ
Global electrophilicity, ω
Ionization potential, I
Electron affinity, A
Chemical hardness, η
Electronegativity, χ
3.5. Quantum Chemical Calculations
reactivity of the ligand. As known both global softness, σ, and
chemical hardness are explained using the energy value of HOMO
and LUMO [118].
We need the quantum chemical parameter to understand the
reaction mechanism. The frontier molecular orbitals HOMO and
LUMO, and also E (band gap; energy difference between HOMO
and LUMO) are very important for molecular activity. HOMO is
the Highest Occupied Molecular Orbital and LUMO is the Lowest
Unoccupied Molecular Orbital. The obtained results are shown in
Table 5.
ꢀ
ꢁ
ELU MO − EHOMO
I − A
η =
σ =
=
(1)
(2)
2
2
HOMO and LUMO tells us from which region of the molecule
it reacts. Energy level of the HOMO is related to the tendency of
donating electron. If a molecule has higher energy level of the
HOMO that would give electron. On the other side, energy level
of the LUMO is related to the tendency of accepting electron. If
a molecule has lower energy level of the LUMO, that would accept
electron. So higher level of the HOMO and lower level of the LUMO
give molecule higher activity.
1
η
The chemical potential of a system, μ, is defined as the deriva-
tive of energy in equilibrium by the number of electrons in fixed
molecular geometry.
EHOMO + ELU MO
μ =
(3)
2
Chemical hardness, η, is resistance to polarization of electron
cloud. Chemical hardness allows the ligand to react with metal
ions of the same hardness level. This gives information about the
Electronegativity, χ, is negative of the chemical potential in
Eq. (4). The global electrophilicity index (ω) is calculated via
8

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Fig. 4. Mass spectra of (a) Pc-6, (b) Pc-7 and (c) Pc-8.
Fig. 5. UV-Visible absorption spectra of (a) Zinc phthalocyanine, Pc-6, (b) Cobalt
(II) phthalocyanine, Pc-7, (c) Nickel (II) phthalocyanine, Pc-8.
Eq. (5).
ꢀ
ꢁ
I + A
χ = −μ =
(4)
(5)
2
two electrochemical techniques. One is cyclic voltammetry (CV)
and second is square wave voltammetry.
χ2
ω =
The left column of the Fig. 9 shows CV voltammograms and
the right column of Fig. 9 shows square wave voltammograms
in DMSO/TBABF4 for metallophthalocyanines. When the cyclic
voltammetry study of Pc-6 compound was examined on the left
coulmn of Fig. 9 (a) it appears to give a reversible reduction pair
called as R1 which has E1/2 value as -1.31 V and a non-reversible
reduction called as R2 which has E1/2 value as -1.73 V. During
the anodic potential screening of the same complex, one non-
reversible oxidation peak called as O1 which has E1/2 value as 0.84
V and one anodic oxidation peak called as O2 which has E1/2 value
as 1.52 V were determined. When the cyclic voltammetry study of
Pc-7 compound was examined on the left coulmn of Fig. 9 (b) it
appears to give a reversible reduction pair called as R1 which has
E1/2 value as -0.57 V and a reversible oxidation peak called as O1
which has E1/2 value as 1.45 V. When the cyclic voltammetry study
2η
Fig. 8 shows HOMO, LUMO, ESP and the optimized geometric
structures of compound 5. The shape of ESP shows on which atom
has more density of electrons on the surface of compound.
3.6. Electrochemical measurements
The voltammograms were recorded by using Parstat 2273 po-
tentiostat/galvanostat. Pt as working electrode, Pt as counter elec-
trode and an Ag/AgCl as reference electrode were used is
a
three electrodes system. Extra pure dimethylsulfoxide as solvent
was used for electrochemical measurements and 0,1 mol/L tetra-
n-butylammoniumtetrafluoroborate as the supporting electrolyte
(TBABF4, 99%) was used. Voltammetric studies were performed in
9

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Fig. 6. (a) The atomic arrangement with atomic labels for the asymmetric unit of compound 5. There are two molecules in the asymmetric unit. While the N1-N2-N3-C9-C8
atoms are exhibiting a five membered ring A, C1—C6 and C11—C16 atoms are exhibiting six-membered rings B and C, respectively. Where, Cg1 is the gravity centre (Cg) of
the five membered ring A, Cg2 and Cg3 represent the gravity centres for the six membered rings B and C, respectively. (b) The monoclinic molecular assembly of compound
5 through the (010) view. Dashed dots indicate the Hydrogen bonds (H•••A).
Fig. 7. (a) The Hirshfeld surfaces in 3D that showing the intermolecular interactions (dnorm), Cg•••Cg interactions (shape index) and relatively flat surfaces (curvedness).
(b) A view of 2D fingerprint plot for the asymmetric unit of the compound 5. Here the C—H•••N contact is the major contributor to the Hirshfeld surface.
which has E1/2 value as 1.80 V. Cyclic voltammetric results of syn-
thesized phthalocyanines were supported by square wave voltam-
metry as it is seen on the right coulmn of Fig. 9 (a), (b) and (c).
3.7. Catalytic oxidation of 2-mercaptoethanol
The catalytic activity of Co(II)phthalocyanines on the oxidation
of 2-mercaptoethanol is a highly studied application in the litera-
ture. Pc-7, Co(II)phthalocyanine, coordinates to the thiolate anion
RS− generated by NaOH and O2 on two axial sides of the central
Co(II) in Pc-7 [48-50]. At this coordinating time, an electron trans-
fer reaction occurs from the thiol to oxygen via the central Co(II).
The resulting thiol radicals combine to form disulfide. Thus, thiol
Fig. 8. HOMO, LUMO, ESP and the optimized geometric structures of compound 5.
compounds are converted to more passive disulfides by this oxida-
tion reaction and lose their reactivity.
Equation (6) shows the reaction between 2-mercaptoethanol
of Pc-8 compound was examined on the left coulmn of Fig. 9 (c) it
appears to give a reversible reduction pair called as R1 which has
E1/2 value as -0.88 V and a reversible oxidation peak called as O1
and oxygen.
4R-S− + O2 → R-S-S-R + 4OH−
(6)
10

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
Fig. 9. Cyclic voltammograms of (a) Pc-6, (b) Pc-7 and (c) Pc-8 on the left and Square wave voltammograms of (a) Pc-6, (b) Pc-7 and (c) Pc-8 on the right.
4. Conclusion
As a result, novel Zn (II), Co (II) and Ni (II) phthalocyanines
were synthesized carrying four triazole groups at peripheral posi-
tions. The well-known Pc synthesize method was used for the di-
rect synthesize of Pc-6, Pc-7 and Pc-8 phthalocyanines. The alkyne
compound, 3, was obtained by reaction of 4-nitrophthalonitrile
and propargyl alcohol in the presence of potassium carbonate at
room temperature. This compound was reacted with azidomethyl
phenyl sulfite, 4, under the catalysis of copper (II) sulfate penta
hydrate and sodium ascorbate to give a triazole compound which
was the click product. The structures of all synthesized compounds
have been fully characterized by combining FT-IR, 1H NMR, 13C
NMR, MALDI-TOF MS, UV-vis spectroscopy and elemental analy-
sis techniques. Electronic absorption spectra have shown that all
phthalocyanines are non-aggregated molecules. Cyclic voltammo-
grams give two reduction reactions and two oxidation reactions
for Pc-6. On the other hand, one reduction reaction and one oxi-
dation reaction for Pc-7 and Pc-8. The catalytic properties of Pc-7,
cobalt(II)phthalocyanine, were investigated in the oxidation reac-
tion of 2-mercaptoethanol with oxygen. Catalytic oxidation of 2-
mercaptoethanol is a widely investigated reaction for the determi-
nation of catalytic activity of phthalocyanines. Turnover number,
initial reaction rate and the oxygen consumption was found in the
Fig. 10. Oxygen consumption in the reaction of catalytic oxidation of 2-
mercaptoethanol by Co(II)phthalocyanine as catalyst.
The ratio of 2-mercaptoethanol and phthalocyanine is 5500:1.
This thiol/catalyst ratio is also quite good in terms of catalytic
work. Yong Pan and others used the ratio of 2-mercaptoethanol
and phthalocyanine was 5000:1 [119]. When NaOH solution is
added, thiol (RSH) will lose proton and convert to thiol (RS-). The
reaction therefore needs a basic environment. Co(II)phthalocyanine
will then begin to catalyze the oxidation reaction of 2-
mercaptoethanol with oxygen. TON, initial rate of reaction and
oxygen consumption were calculated respectively as 18.09, 0.12
μmol.s−1, 6.88 μmol.min−1 and change in oxygen consumption
over time is shown in Fig. 10.
catalytic oxidation of 2-mercaptoethanol as 18.09, 0.12 μmol.s−1
6.88 μmol.min−1 respectively.
,
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
11

H. Karaca, N.Ç. Delibas¸, S. Sag˘lam et al.
Journal of Molecular Structure 1236 (2021) 130225
CRediT authorship contribution statement
[20] G.D. Sharma, P. BalaRaju, M.S. Roy, Effect of functional groups of acceptor ma-
terial on photovoltaic response of bulk hetero-junction organic devices based
on tin phthalocyanine (SnPc), Solar Energy Materials and Solar Cells 92 (3)
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Hüseyin Karaca: Conceptualization, Funding acquisition, Inves-
tigation, Methodology, Software, Validation, Visualization, Writing -
original draft, Writing - review & editing. Nagihan Çaylak Delibas¸:
Conceptualization, Supervision. Serap Sag˘lam: Writing - original
draft. Hasan Pis¸kin: Methodology, Writing - original draft. Serdar
Sezer: Conceptualization, Supervision. Tuncer Hökelek: Conceptu-
alization, Supervision. Murat Teker: Supervision.
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