Peripherally 1,2-dinaphthyl ethanediol substituted phthalocyanine complexes: Synthesis, characterization, aggregation, and application in benzyl alcohol oxidation at room temperature

Article abstract of DOI:10.3906/kim-1903-71

In this study, the synthesis of a novel 1,2-dinaphthyl ethanediol substituted phthalonitrile (2) together with tetra-substituted zinc(II) phthalocyanine (Pc) (3) and cobalt(II) Pc (4) bearing 1,2-dinaphthyl ethanediol at peripheral positions was described

Full text of DOI:10.3906/kim-1903-71

Turk J Chem
Turkish Journal of Chemistry
(2019) 43: 1017 – 1029
© TÜBİTAK
http://journals.tubitak.gov.tr/chem/
doi:10.3906/kim-1903-71
Research Article
Peripherally 1,2-dinaphthyl ethanediol substituted phthalocyanine complexes:
synthesis, characterization, aggregation, and application in benzyl alcohol
oxidation at room temperature
Halil Zeki GÖK1,∗,, Mustafa Kemal YILMAZ ,
2
1
Department of Biomedical Engineering, Bucak Faculty of Technology, Burdur Mehmet Akif Ersoy University,
Bucak, Burdur, Turkey
Department of Chemistry, Faculty of Arts and Sciences, Mersin University, Mersin, Turkey
2
Received: 27.03.2019
•
Accepted/Published Online: 20.06.2019
•
Final Version: 06.08.2019
Abstract: In this study, the synthesis of a novel 1,2-dinaphthyl ethanediol substituted phthalonitrile (2) together with
tetra-substituted zinc(II) phthalocyanine (Pc) (3) and cobalt(II) Pc (4) bearing 1,2-dinaphthyl ethanediol at peripheral
positions was described. The aggregation behaviors of metallophthalocyanines 3 and 4 in solution were investigated by
carrying out Beer–Lambert experiments at different concentrations. In addition, the catalytic activity of new cobalt(II)
Pc 4 was investigated for benzyl alcohol oxidation. Benzyl alcohol was converted to benzaldehyde using cobalt(II) Pc
4 as a catalyst by a conversion of 99% with selectivity of 100% at room temperature in 1 h. Several spectroscopic
1
13
techniques such as FT-IR, UV-Vis, H and C NMR, and MALDI-TOF MS were used for the characterization of the
newly synthesized compounds.
Key words: Metallophthalocyanine, catalysis, C2 -symmetric, benzyl alcohol oxidation, aggregation
1. Introduction
Phthalocyanines (Pcs) are one of the most popular chemical materials studied in chemistry and have been
applied widely in advanced technologies due to the unique properties of Pcs such as chemical and thermal
stability, electron transfer ability, UV-Vis light absorption, and high molar absorption coefficients [1]. Pcs
can be synthesized either in polymeric form or monomeric form by using bis-phthalonitrile or phthalonitrile
derivatives, respectively, in the presence or absence of metal ions [2–4]. Monomeric or polymeric Pcs have been
widely used in many research areas, such as catalysts for many chemical reactions [5], precious metal recovery
[6], and conversion of solar energy to electric power [7].
Catalysis is another attractive area for both scientific researchers and industrial applications, and one of
the most important applications for Pc metal complexes as well [8]. For instance, production of aldehydes from
their corresponding alcohols involves catalytic oxidation of alcohols in the presence of Pcs with redox active
metal centers such as cobalt and iron [9]. The solubility of a Pc compound in solvent used for oxidation reaction
determines its usability as a catalyst in catalytic oxidation. The solubility of Pc compounds can be improved
by incorporation of various substituents to either the nonperipheral or peripheral positions of the Pc skeleton.
This appropriation is one of the most used synthetic strategies to obtain highly soluble and nonaggregated Pc
metal complexes [10–18].
∗Correspondence: halilzekigok@gmail.com
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This work is licensed under a Creative Commons Attribution 4.0 International License.

GÖK and YILMAZ/Turk J Chem
The aim of the present work was to synthesize a phthalonitrile precursor derived from sterically hin-
dered phenols. The 1,2-di(naphthalen-1-yl)ethane-1,2-diol unit of Pc, an analog of 1,2-diphenylethane-1,2-diol
(hydrobenzoin), was chosen because of being sterically hindered and straightforwardly accessible. It was antic-
ipated that this would result in Pcs containing bulky substituents placed at sites where they can interfere best
with cofacial self-association and therefore enhance solubility. A reduction in the tendency of Pcs to aggregate
in solution could be advantageous in a number of applications, including catalytic applications [15]. Catalytic
activity of cobalt(II) Pc 4 in benzyl alcohol oxidation was also examined, with the aim of improving the ben-
zaldehyde selectivity and increasing the range of products, and comparing their catalytic activity in the presence
of different oxidants at different temperatures. Moreover, other factors affecting benzyl alcohol oxidation, such
as solvent type, substrate to catalyst ratio, and oxidant amount, were also discussed in this work.
2. Experimental
2.1. Materials and methods
1,2-Dinaphthyl ethanediol and 4-nitrophthalonitrile were prepared by following the procedures given in the lit-
erature, respectively [19,20]. The reagents and solvents used during this study were purchased from commercial
suppliers. Drying and purification of all solvents was performed according to the procedures given by Perrin
and Armarego [21]. The purification of compounds was carried out on silica gel (Merck, Kieselgel 60, 400–630
mesh).
A PerkinElmer Spectrum 65 spectrometer, Varian Mercury 400 MHz spectrometer, Micromass Quatro
LC/ULTIMA LC-MS/MS and Bruker Daltonics MALDI-TOF spectrometer, a PG-T80+ spectrophotometer,
and a LECO Elemental Analyzer were used to record the spectral data of the newly synthesized compounds. The
KBr pellet technique was used for the FT-IR measurements. NMR spectra were collected using CDCl3 and THF-
d8 (99.9%). UV-Vis measurements were performed at room temperature in 1-cm path-length cuvettes. The
melting points of the compounds were determined on a melting point apparatus and are reported uncorrected.
The gas chromatography analyses were monitored on a Shimadzu GC-2010 Plus gas chromatograph.
2.2. Synthesis
2.2.1. 4-(2-Hydroxy-1,2-dinaphtylethoxy)phthalonitrile (2)
4-Nitrophthalonitrile (0.28 g; 1.6 mmol) was added to stirring DMSO (3.0 mL) containing 1,2-dinaphthyl
ethanediol (1) (0.5 g, 1.6 mmol) under nitrogen atmosphere at room temperature and stirred for a further
15 min. Then oven-dried finely ground K2 CO3 (0.22 g; 1.6 mmol) was added to the stirring reaction mixture
at room temperature and the resulting mixture was kept stirring for a further 3 h. The reaction medium
was monitored by thin-layer chromatography. At the end of 3 h, the reaction mixture was transferred to a
beaker containing 1 portion of water and 3 portions of ice. The precipitate formed in the beaker was separated
by vacuum filtration. This precipitate was extracted with dichloromethane and water. The organic phases
were combined and then dried over anhydrous Na2 SO4 . By filtration, sodium sulfate was separated from the
organic phase. The solvent was evaporated under reduced pressure in order to obtain the crude product. The
purification of the crude product was performed on silica gel by flash column chromatography. Dichloromethane
was used as the mobile phase and the target product was obtained as a white solid. Yield: 0.59 g, (83%); mp:
115–116 ◦ C. Anal. Calc. C30 H20 N2 O2 : C 81.80%, H 4.58%, N, 6.36%. Found: C 81.93%, H 4.66%, N 6.37%.
FT-IR (KBr disk) vmax /cm−1 : 3473, 3416 (OH), 3049, 2931, 2230 (C≡N), 1712, 1596, 1561, 1490, 1294, 1249,
1018

GÖK and YILMAZ/Turk J Chem
1
1092, 1041, 778, 735; H NMR (400 MHz, CDCl3 , ppm) δ: 7.89 (d, J = 8.4 Hz, H), 7.79 (d, J = 8.4 Hz, H),
7.75–7.67 (m, 4H), 7.62 (d, J = 7.0 Hz, H), 7.50–7.46 (m, 2H), 7.42–7.26 (m, 2H), 7.07 (dd, J = 8.9 Hz, J = 2.2
13
Hz, H), 6.22 (d, J = 6.4 Hz, H), 6.01 (d, J = 6.4 Hz, H), 3.12 (br, s, OH); C NMR (100 MHz, CDCl3 , ppm)
δ: 160.7, 135.2, 134.1, 133.7, 133.6, 130.8, 130.7, 130.3, 129.8, 129.2, 128.7, 126.6, 125.9, 125.6, 125.4, 125.0,
124.9, 122.8, 121.2, 120.1, 117.3, 115.4, 115.0, 82.7, 74.5; MS (ESI¯) MS Calc.: 475.1; Found: 475.1 [M + Cl]−
.
2.2.2. 2(3),9(10),16(17),23(24)-Tetrakis-{(2-hydroxy-1,2-dinaphtylethoxy)}phthalocyaninato
zinc(II) (3)
A Schlenk tube containing 4-(2-hydroxy-1,2-dinaphtylethoxy)phthalonitrile (2) (0.22 g; 0.5 mmol), anhydrous
Zn(CH3 CO2)2 (0.046 g; 0.25 mmol), a catalytic amount of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and 2.5
mL of n-pentanol as reaction solvent was heated to 140 ◦ C for 24 h under inert atmosphere to give the desired
zinc(II) Pc compound (3). At the end of 24 h, the reaction mixture was cooled to room temperature. The
reaction mixture was transferred to an evaporating flask and the solvent of the reaction mixture was removed
under reduced pressure. The remaining green crude product was purified by silica gel column chromatography
with methanol followed by a chloroform-methanol (98:2) solvent system as eluting solvents. Further purification
of compound 3 was performed by preparative thin-layer silica gel chromatography with a methanol-chloroform
(2:98) solvent system. Yield was 0.026 g (12%). mp: >300 ◦ C. IR (KBr disk) νmax /cm−1 : 3557, 3381 (OH),
1
3030, 2922, 1611, 1484, 1395, 1335, 1223, 1090, 1050, 1008, 836, 763, 738, 696. H NMR (400 MHz, d8 -THF,
ppm) δ: 7.80–7.31 (m, 68H), 6.00 (m, 4H), 5.46 (m, 4H); UV-Vis (DMF): λmax , nm (log ε): 356 (5.13), 616
+
+
(4.69), 684 (5.43); MALDI-TOF (ESI ) (m/z): Calc.: 1824.5; Found: 1824.5 [M] .
2.2.3. 2(3),9(10),16(17),23(24)-Tetrakis-{(2-hydroxy-1,2-dinaphtylethoxy)}phthalocyaninato
cobalt(II) (4)
Cobalt(II) Pc (4) was synthesized by following the procedure for 3. For this purpose, CoCl2 was used instead
of Zn(CH3 CO2)2. The amount of CoCl2 was 0.035 g. Purification: Flash column chromatography on silica
gel with a solvent mixture of diethyl ether-hexane (8:2), then methanol-chloroform (1:99). Yield was 0.030 g
(14%); mp: >300 ◦ C. IR (KBr disk) νmax /cm−1 : 3553, 3415 (OH), 3059, 3030, 2901, 1610, 1520, 1482, 1407,
1342, 1276, 1230, 1098, 1066, 1006, 835, 755, 696; UV-Vis (DMF): λmax , nm (log ε): 326 (5,25), 610 (4.82),
+
672 (5.38); MS (MALDI-TOF) (m/z): Calc.: 1819.5; Found: 1819.3 [M] .
2.3. Procedure for the application of cobalt(II) Pc (4) in benzyl alcohol oxidation
Cobalt(II) Pc (4) as a catalyst, benzyl alcohol, and solvent were put together in a standard Schlenk tube. To
remove oxygen, nitrogen gas was bubbled into the Schlenk tube. The oxidant was then added to the Schlenk tube
and the resulting reaction mixture was stirred for the desired time. Monitoring of the reaction and calculation of
the conversion amount of the benzyl alcohol to benzaldehyde was performed by comparison of 1,4-benzoquinone,
benzaldehyde, and benzoic acid standards on a Shimadzu GC-2010 Plus gas chromatograph equipped with a
30 m × 0.25 mm × 0.25 µm capillary column (Rxi - 5ms, 95% diphenyl, 95% dimethyl polysiloxane).
1019

GÖK and YILMAZ/Turk J Chem
3. Results and discussion
3.1. Synthesis and characterization
The synthetic pathway for the synthesis of phthalonitrile 2 and its Pc derivatives 3 and 4 is given in the
Scheme. Obtaining phthalonitrile derivative 2 was the first step of the synthetic pathway. The reaction
of 1,2-dinaphthyl ethanediol (1) with 4-nitrophthalonitrile in a flask containing K2 CO3 as the base and
DMSO as the solvent of the reaction afforded substituted phthalonitrile derivative 2, namely 4-(2-hydroxy-
1,2-dinaphtylethoxy)phthalonitrile, with a yield of 83%.
Scheme. Syntheses of phthalonitrile derivative 2 and metallo-Pcs 3 and 4. Reagents and conditions: (i) DMSO,
K2 CO3 , rt; (ii) Zn(CH3 COO)2 , n-pentanol, DBU, 140 ◦ C; (iii) CoCl2 , n-pentanol, DBU, 140 ◦ C.
The characterization of new phthalonitrile compound 2 was done first by IR spectrum. The IR spectrum
of 2 showed the vibration bands for C≡N at 2230 cm−1 and OH at 3473 and 3416 cm−1 , respectively, which
is in agreement with the structure of 2. The disappearance of strong stretching vibration bands of –NO2 in the
1020

GÖK and YILMAZ/Turk J Chem
1
IR spectrum of 2 confirmed the formation of 2 as well (see Supplementary Figure 1). The H NMR spectrum
acquired in CDCl3 (see Supplementary Figure 2) gave us the opportunity to characterize the structure of 2.
The broad singlet that appeared at δ = 3.12 ppm was attributed to the –OH group of 2. The aliphatic –CH
protons of 2 were expected to give two separate doublets with the same coupling constant. The observation of
peaks at 6.22 and 6.01 ppm with a coupling constant of J = 6.4 Hz was in agreement with our expectations.
The other sets of protons corresponding to the naphthyl moieties appeared together between 7.90 and 7.07 ppm.
13
Structural characterization of the same compound was additionally performed by C (APT) NMR spectrum.
Carbon resonances of the nitrile carbons that substituted the benzene moiety appeared as two peaks at δ =
13
115.4 and 115.0 ppm due to the C1 symmetry of phthalonitrile derivative 2 in the C (APT) NMR spectrum
(see Supplementary Figure 3). The carbon resonances observed at δ = 82.7 and 74.5 ppm were attributed to
CH carbons containing a hydroxyl group and oxygen atom, respectively, confirming the proposed structure.
+
In the ES/MS spectrum of 2, the expected molecular ion peak appeared at m/z = 475.1 [M + Cl] (see
Supplementary Figure 4), which is in agreement with the proposed formula.
In a Schlenk tube containing 2.5 mL of n-pentanol and a catalytic amount of DBU, the cyclotetrameriza-
tion reaction of 4-(2-hydroxy-1,2-dinaphtylethoxy)phthalonitrile 2 with metal salts Zn(CH3 CO2)2 and CoCl2
ZnPc (3)
CoPc (4)
0,8
0.4
0
1.2
0.8
0.4
0
Chloroform
Chloroform
Dimethylformamide
Dichloromethane
Tetrahydrofuran
Dimethylformamide
Dichloromethane
Tetrahydrofuran
300
400
500
600
700
800
300
400
500
600
700
800
Wavelenght (nm)
Wavelenght (nm)
Figure 1. UV-Vis spectra of zinc(II) Pc (3) and cobalt(II) Pc (4) in different solvents.
ZnPc (3) in DMF
CoPc (4) in DMF
2.5
2.4
2
2
1.6
1.2
0.8
0.4
0
1.5
1
2E-6M
2E-6M
4E-6M
8E-6M
10E-6M
4E-6M
8E-6M
10E-6M
0.5
0
300
400
500
600
700
800
300
400
500
600
700
800
Wavelenght (nm)
Wavelenght (nm)
Figure 2. Aggregation properties of Pc complexes 3 and 4 at different concentrations in DMF.
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GÖK and YILMAZ/Turk J Chem
afforded peripherally substituted metallo-Pcs 3 and 4, respectively. Flash silica gel column chromatography
and/or preparative thin-layer chromatography using silica gel were applied to the crude Pc products in order to
1
remove impurities. Pc complexes were characterized by a combination of FT-IR, UV-Vis, H NMR (for com-
pound 3), and MALDI-TOF techniques. In the IR spectra of 3 and 4 (see Supplementary Figure 5 for 3 and
Supplementary Figure 8 for 4), the vibration at around 2230 cm−1 related to the C≡N group was not observed
after the cyclotetramerization of phthalonitrile derivative 2, which confirms the formation of the desired Pc
compounds. The IR spectra of 3 and 4 are very similar, but small shifts in wavenumbers were observed. The
–OH group of metallo-Pcs 3 and 4 was characterized by a vibration band at 3381 cm−1 for 3 and 3415 cm−1
1
in their IR spectra. The H NMR spectrum of 3 showed expected protons between at δ = 7.80–5.46 ppm.
1
The interpretation of the H NMR spectrum of 3 was a challenge due to the overlapped peaks of Pc and the
1
attached naphthyl moiety. Thus, multiplet analysis was used for the integration of the peaks in the H NMR
1
spectrum of 3 (see Supplementary Figure 6). In the case of the cobalt(II) Pc (4), the H NMR spectrum of
4 could not be collected since the cobalt(II) ion is paramagnetic [22]. The mass measurements of Pcs 3 and 4
were performed by using MALDI-TOF techniques. The mass spectra of 3 and 4 showed expected molecular ion
+
+
peaks at m/z = 1824.5 [M] for 3 and m/z = 1819.3 [M] for 4, which agree with the proposed structures
(see Supplementary Figure 7 for 3 and Supplementary Figure 9 for 4).
The solubility of metallo-Pcs 3 and 4 in common organic solvents such as CH2 Cl2 , CHCl3 , DMF, and
THF is good enough to investigate their aggregation properties in those solvents. Hence, the electronic spectra
of Pc complexes 3 and 4 were recorded in those solvents at a concentration of 4 × 10−6 M in order to compare
the effect of solvent on the position and absorption of Q bands of synthesized metallo-Pcs 3 and 4. The recorded
spectra can be seen in Figure 1.
The appearance of Q bands as unsplit and single in the recorded UV-Vis spectra of 3 and 4 confirmed
the D4h symmetry of 3 and 4, which is expected for Pcs containing a metal in their center [23]. The absorptions
related to Q bands of 3 and 4 were observed at 684 and 672 nm with shoulders at 616 and 610 nm, respectively,
while the B band was at 356 and 326 nm in the recorded UV-Vis spectra in DMF, respectively. It is well known
in the literature that the increasing size of the central metal [24] and number of electrons in the d-orbitals [25]
cause a redshift in the Q band. A smaller HOMO-LUMO gap in zinc(II) Pcs than cobalt(II) Pcs causes the
larger redshift for the Q band in zinc(II) Pc 3 than that of 4. If the UV-Vis spectra of 3 in CHCl2 and 4 in
CHCl3 and CHCl2 are carefully reviewed, it can be seen that the shape of the main Q bands broadened, and
the intensity of the main Q bands decreased in the recorded UV-Vis spectra of 3 and 4. These kinds of changes
for the main Q band are referred to as aggregation, the reason for which is the presence of dimers or higher
order complexes of Pcs [26–28].
To investigate the aggregation behavior of synthesized Pc complexes 3 and 4 in solution, Beer-Lambert
experiments were performed with Pc complexes 3 and 4 at concentrations in the range of 10 × 10−6 to 2 ×
10−6 mol dm−3 by scanning the spectral window between 300 and 800 nm on a UV-Vis spectrophotometer.
From the results of the experiment, it is clearly seen from Figure 2 that the absorption intensity of the main
Q band of 3 and 4 increased by increasing the concentration of the solution containing Pc compounds. These
results confirmed that there were no new bands blue-shifted due to the presence of aggregated species for Pc
compounds 3 and 4 [29].
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GÖK and YILMAZ/Turk J Chem
3.2. Application of cobalt(II) Pc (4) in benzyl alcohol oxidation
In a typical run, the cobalt(II) Pc (4) as catalyst, benzyl alcohol, and solvent were placed in a Schlenk tube.
To remove the oxygen, nitrogen gas was bubbled into the Schlenk tube. The oxidant was then added to the
reaction mixture and the resulting reaction mixture was stirred for 1 h at the desired temperature. Monitoring
of the reaction and calculation of the conversion amount of the benzyl alcohol to benzaldehyde was performed
by comparison of standards on a Shimadzu GC-2010 Plus gas chromatograph.
a
Table 1. Solvent, oxidant, and temperature effect on the oxidation of benzyl alcohol with complex 4 *.
Temp. Total conversion Benzaldehyde Benzoic acid 1,4-Benzoquinone Selectivity
c
Entry Solvent Oxidant
TON
b
(◦C)
80
(%)
21
89
100
100
100
100
100
99
(%)
18
37
86
83
8
95
95
99
(%)
-
-
-
17
92
-
-
-
(%)
-
-
11
-
(%)
86
41
86
83
8
95
95
100
1
2
3
4
5
6
7
8
DMF
DMF
ACN
ACN
ACN
ACN
ACN
ACN
TBHP
42
m-CPBA 80
TBHP 80
m-CPBA 80
178
200
200
200
200
200
198
H2O2
80
60
40
25
-
TBHP
TBHP
TBHP
4
3
-
a
Reaction conditions: benzyl alcohol (2.90 × 10−4 mol), oxidant (2.90 × 10−4 mol), catalyst (1.45 × 10−6 mol), solvent
b
5.0 mL. Reactions were conducted for 1 h in all cases. Conversions were determined by GC based on benzyl alcohol.
c
Turnover number (TON: moles of substrate converted per mole of metal in the catalyst). *GC chromatograms related
to Table 1 can be found in the Supplementary file.
To evaluate the catalytic activity of complex 4, the effects of solvent, oxidant, reaction temperature,
oxidant to catalyst ratio (O/C), and substrate to catalyst ratio (S/C) were investigated on the selective oxidation
of benzyl alcohol to benzaldehyde. For initial tests, the molar ratio of catalyst, oxidant, and benzyl alcohol was
chosen as 1/200/200 and reaction time was kept constant for 1 h at 80 ◦ C. The influence of the solvent, oxidant,
and reaction temperature was first determined and the results are illustrated in Table 1. After screening the effect
of the solvent, we found 89% conversion but poor selectivity (41%) for 1 h of the reaction in dimethylformamide
(DMF) when m-chloroperoxybenzoic acid (m-CPBA) was used as an oxidant (entry 2). With the same oxidant,
good benzaldehyde selectivity (83%) was obtained in acetonitrile (ACN) with a full conversion when comparing
the result obtained from DMF as solvent (entries 2 and 4). When tert-butylhydroperoxide (TBHP) was used as
an oxidant, total conversion was very poor in DMF (entry 1). On the other hand, complete conversion and better
selectivity (86%) were obtained in ACN when TBHP was used as oxidant, but the formation of benzoquinone
was also observed (entry 3). In all cases, the use of ACN as a solvent gave better conversion and selectivity
compared to DMF as it allows for the higher solubility of the substrate and catalyst used depending on the high
polarity. Otherwise, in the presence of hydrogen peroxide (H2 O2) as an oxidant in ACN, oxidation of benzyl
alcohol gave benzaldehyde as the minor product while benzoic acid was the major (92%, entry 5). It is noted
that the color of the reaction went from the blue of the catalyst to colorless suddenly following the addition of
H2 O2 ; therefore, the catalytic process was not studied effectively in the presence of this oxidant. This situation
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GÖK and YILMAZ/Turk J Chem
is probably due to the degradation of the CoPc catalyst (4) by the oxidant at the beginning of the reaction.
Besides that, a control experiment was carried out in the absence of oxidant, and benzyl alcohol was not oxidized
to related corresponding products. After determining the best solvent and oxidant, we decided to investigate the
role of the reaction temperature on the oxidation of benzyl alcohol. Therefore, three experiments were done at
different temperatures in the range of 25–80 ◦ C (entries 6–8). Normally, the reaction temperature has a strong
influence on the oxidation of benzyl alcohol and the reaction rate is also reduced due to decrease in reaction
temperature [30]. Surprisingly, decreasing temperature did not affect the total conversion of benzyl alcohol,
and due to the decrease in temperature benzaldehyde selectivity was gradually increased and finally reached
100% (compare entries 3 and 6–8). Thus, room temperature was chosen to be the optimum temperature to
achieve the highest benzaldehyde selectivity for our catalyst. Under the framework of this study, the successful
application of CoPc as an oxidation catalyst for the selective oxidation of benzyl alcohol to benzaldehyde at
room temperature with only 1 h of the reaction was achieved.
To extend the catalytic tests of catalyst 4, the effect of the oxidant amount on the selective oxidation
of benzyl alcohol was also studied by varying the oxidant to catalyst ratio from 100/1 to 900/1 while other
parameters were kept constant (Table 2). We found that increasing the oxidant to catalyst ratio from 100/1 to
200/1 led to the selective oxidation of benzyl alcohol to benzaldehyde with total conversion of 99% and 100%
selectivity (TON = 198), but further increasing the oxidant ratio led to a decrease in the catalytic activity
(up to 27%) (compare entries 1–7). These results support that in the presence of a higher amount of oxidant,
the active sites of cobalt ion are blocked and this effect leads to the generation of inactive intermediate species
during the catalytic reaction [31–36].
a
Table 2. The effect of oxidant amount on benzyl alcohol oxidation with complex 4 *.
Oxidant/ Total conversion Benzaldehyde Benzoic acid 1,4-Benzoquinone Selectivity
c
Entry
TON
b
catalyst
100/1
200/1
300/1
400/1
500/1
700/1
900/1
(%)
82
99
58
45
34
29
27
(%)
68
99
46
41
34
29
26
(%)
10
-
11
3
-
(%)
-
-
1
1
-
-
-
(%)
83
100
79
91
100
100
96
1
2
3
4
5
6
7
164
198
116
90
68
58
-
-
54
a
Reaction conditions: benzyl alcohol (2.90 × 10−4 mol), oxidant (TBHP), catalyst (1.45 × 10−6 mol), acetonitrile
(5.0 mL), 25 ◦C, time: 1 h. Conversions were determined by GC based on benzyl alcohol. Turnover number (TON:
moles of substrate converted per mole of metal in the catalyst). *GC chromatograms related to Table 2 can be found
in the Supplementary file.
b
c
For the amounts of catalyst used influencing the results of the selective oxidation of benzyl alcohol, the
effect of substrate to catalyst ratio was also investigated by varying from 200/1 to 1500/1 under optimized
conditions (Table 3). First of all, a blank experiment was carried out under the optimized conditions without
catalyst for comparison, and we did not observe any benzaldehyde formation in the reaction mixture (entry 1).
The results show that benzyl alcohol was converted to benzaldehyde with full conversion and 96% selectivity,
achieving a TON of 400, even when the substrate to catalyst ratio was 400/1 (entry 3). On further increasing
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GÖK and YILMAZ/Turk J Chem
the substrate to catalyst ratio, the catalytic activity decreased for the oxidation of benzyl alcohol, as expected
(entry 4–7). This study showed that a 400/1 ratio of substrate to catalyst was needed for the oxidation of
benzyl alcohol to get complete conversion and high selectivity.
a
Table 3. The effect of substrate to catalyst ratio on benzyl alcohol oxidation with complex 4 *.
Substrate/ Total conversion Benzaldehyde Benzoic acid 1,4-Benzoquinone Selectivity
c
Entry
TON
b
catalyst
200/1
(%)
-
(%)
-
(%)
(%)
-
(%)
-
d
1
2
3
4
5
6
7
-
-
-
-
-
-
-
-
200/1
400/1
600/1
800/1
1000/1
1500/1
99
100
53
32
17
9
99
96
52
31
16
9
-
100
96
98
96
94
99
198
400
318
256
170
135
2
1
-
-
-
a
Reaction conditions: benzyl alcohol, TBHP (2.90 × 10−4 mol), catalyst (1.45 × 10−6 mol), acetonitrile (5.0 mL),
25 ◦C, time: 1 h. Conversions were determined by GC based on benzyl alcohol. Turnover number (TON: moles
of substrate converted per mole of metal in the catalyst). Without catalyst. *GC chromatograms related to Table 3
can be found in the Supplementary file.
b
c
d
Table 4 was summarized by catalytic activity studies of some previously reported CoPc catalysts sub-
stituted with peripheral units for the oxidation of cyclohexene or benzyl alcohol. Additionally, Çakır et al.
investigated the catalytic performance of (2-{2-[3-(diethylamino)phenoxy]ethoxy}ethoxy) substituted Fe(II)
and Co(II) phthalocyanines on selective oxidation of benzyl alcohol in ACN at 70 ◦ C. Product conversion of
94% and 77% benzaldehyde selectivity were obtained using FePc as catalyst under their optimized conditions in
Table 4. Catalytic activities towards the oxidation of benzyl alcohol and cyclohexene of some previously reported CoPc
catalysts.
React. React.
Catalyst
Substrate
Oxidant Conversion (%) Selectivity (%) Ref.
time
(h)
24
temp.
(◦C)
25
a
Co(tbpcH2) cyclohexene
O2
30
92
98
97
99
nr
60
68
86
[39]
[31]
b
f
f
g
CoPc
cyclohexene
3
90
TBHP
c
CoPc
d
CoPc
CoPc
Benzyl alcohol
Benzyl alcohol
3
1
50
25
TBHP
TBHP
[9]
-
e
g
100
a
b
tbpcH2: tetra-tert-butylphthalocyanine.
Pc: tetrakis-[2-(1,4-dioxa-8-azaspiro[4.5]dec-8-yl)ethoxy]phthalocyanine.
Pc: tetrakis-(3,3-diphenylpropoxy)phthalocyanine.
Pc: {2-[2-(2,3,5,6-tetrafluorophenoxy)ethoxy]ethoxy}phthalocyanine.
Pc: {1,2-di(naphthalen-1-yl)ethane-1,2-diol}phthalocyanine.
for 2-cyclohexene-1-ol.
c
d
e
f
g
for benzaldehyde.
nr: not reported.
1025

GÖK and YILMAZ/Turk J Chem
3 h of reaction [30]. Özer et al. reported the catalytic behavior of novel Co(II) and Pd(II)-perfluoroalkyl Pc com-
plexes for benzyl alcohol oxidation in perfluoromethylcyclohexane (PFMCH) or using different organic-fluorous
biphasic systems such as n-hexane-PFMCH, acetone-PFMCH, and toluene-PFMCH. They tested the selective
oxidation of benzyl alcohol with TBHP, H2 O2 , m-CPBA, aerobic O2 , and oxone as oxidants and they found
that TBHP was the best one. They also tested the effect of reaction temperature using 1.24 × 10−2 mol TBHP
with substrate/catalyst ratio of 520 for CoPc in an n-hexane-PFMCH system. After 24 h, they obtained 92.7%
aldehyde selectivity with only 39.4% total conversion between 30 and 70 ◦ C [37]. Kamiloğlu et al. investigated
catalytic activity of tetra-{2-(2,3,5,6-tetrafluorophenoxy)ethoxy} substituted Co(II) and Fe(II)Pc complexes
for the oxidation of benzyl alcohol, changing different parameters to determine the optimal conditions. They
observed that for this catalyst system, TBHP was the best oxidant and the maximum conversion was obtained
(95%) with product distribution of 74% benzaldehyde, 5% benzoquinone, and 16% benzoic acid at 50 ◦ C for
the Co(II)Pc complex in 3 h [38]. Based on the performance of our 1,2-dinaphthyl ethanediol substituted
CoPc catalyst towards benzyl alcohol oxidation, it can be said that it is a more successful catalyst than some
other catalysts mentioned above. The best reported results were obtained in terms of reaction temperature (25
◦ C), reaction time (1 h), and benzaldehyde selectivity (100%) in literature for oxidation of benzyl alcohol with
TBHP as an oxidant. On the other hand, the presence of a bulky 1,2-di(naphthalen-1-yl)ethane-1,2-diol group
on the Pc unit seems to enhance the product selectivity and catalyst activity, possibly due to the increased
steric crowding in CoPc complex 4. In addition to the overall rating, improved conversions and activities were
achieved while milder reaction conditions were employed compared to the previously reported complexes.
3.3. Conclusions
This study describes the synthesis of a novel phthalonitrile, 4-(2-hydroxy-1,2-dinaphtylethoxy)phthalonitrile,
and its zinc(II) and cobalt(II) Pc derivatives. All synthesized compounds were characterized by using spec-
1
13
troscopic techniques such as FT-IR, UV-Vis, H and C NMR, and mass analysis. Pc complexes 3 and 4
were examined to understand the aggregation behavior in different organic solvents by using Beer–Lambert
experiments. The experiments showed that the zinc(II) Pc 3 and cobalt(II) Pc 4 did not exhibit any aggre-
gation behavior in DMF and THF solvent at concentrations of 10 × 10−6 and 2 × 10−6 mol dm−3 . In
addition to that, the catalytic performance of cobalt(II) Pc 4 was investigated in benzyl alcohol oxidation.
Reaction conditions such as oxidant and solvent type, reaction temperature, substrate to catalyst ratio, and
oxidant to catalyst ratio were investigated in an effort to establish optimum catalytic conditions. The most
exciting observation is that benzaldehyde was found as a major product in all of the catalytic tests. Also, the
optimization studies showed that benzyl alcohol gave benzaldehyde with full selectivity in only 1 h of reaction
at room temperature using an oxidant/substrate/catalyst ratio of 200/200/1 in the presence of 4-(2-hydroxy-
1,2-dinaphtylethoxy)phthalonitrile substituted cobalt(II) Pc (4).
Acknowledgments
Dr. Yaşar Gök from Burdur Mehmet Akif Ersoy University and İlker Ümit Karayiğit from Osmaniye Korkut
Ata University are greatly acknowledged for their technical assistance with synthesis studies.
1026

GÖK and YILMAZ/Turk J Chem
References
1. Leznoff DCC, Lever ABP. Phthalocyanines: Properties and Applications, Vols. 1-4. Weinheim, Germany: Wiley-
VCH, 1998.
2. Gök Y, Gök HZ. Synthesis, characterization and spectral properties of novel zinc phthalocyanines derived from C2
symmetric diol. Journal of Molecular Structure 2014; 1067: 169-176. doi: 10.1016/j.molstruc.2014.03.037
3. Bilgin A, Mendi A, Yıldız U. Novel phthalocyanine polymers with very flexible pentathiatetraethylene units.
Polymer 2006; 47 (26): 8462-8473. doi: 10.1016/j.polymer.2006.10.018
4. Bilgin A, Yağcı Ç, Mendi A, Yıldız U. Novel network polymeric phthalocyanines: synthesis and characterization.
Macromolecular Chemistry and Physics 2005; 206 (22): 2257-2268. doi: 10.1002/macp.200500341
5. Zalomaeva OV, Ivanchikova ID, Kholdeeva OA, Sorokin AB. Kinetics and mechanism of the oxidation of alkyl
substituted phenols and naphthols with tBuOOH in the presence of supported iron phthalocyanine. New Journal
of Chemistry 2009; 33: 1031-1037. doi: 10.1039/B821534K
6. Gök HZ, Gök Y. A novel polymeric phthalocyanines bridged flexible 1,5-pentanedithiol unit for metal ions
extraction: synthesis, characterization and evaluation, Journal of Inclusion Phenomena and Macrocyclic Chemistry
2019; 94: 55-63. doi: 10.1007/s10847-019-00901-1
7. Cho KT, Trukhina O, Roldán-Carmona C, Ince M, Gratia P et al. Molecularly engineered phthalocyanines as hole-
transporting materials in perovskite solar cells reaching power conversion efficiency of 17.5%. Advanced Energy
Materials 2017; 7: 1601733. doi: 10.1002/aenm.201601733
8. Sorokin AB. Phthalocyanine metal complexes in catalysis. Chemical Reviews 2013; 113: 8152-8191. doi: 10.1021/
cr4000072
9. Aktaş A, Acar İ, Saka ET, Bıyıklıoğlu Z. Synthesis of polyfluoro substituted Co(II), Fe(II) phthalocyanines and
their usage as catalysts for aerobic oxidation of benzyl alcohol. Journal of Organometallic Chemistry 2016; 815-816:
1-7. doi: 10.1016/j.jorganchem.2016.04.025
10. Matlou GG, Kobayashi N, Kimura M, Nyokong T. Physicochemical properties of water soluble unsymmetrical
phthalocyaninefolic acid conjugates. Dyes and Pigments 2018; 149: 393-398. doi: 10.1016/j.dyepig.2017.10.030
11. Winckel E, David B, Moreno MS, Gonzalez-Delgado JA, Escosura A et al. Octacationic and axially di-substituted
silicon (IV) phthalocyanines for photodynamic inactivation of bacteria. Dyes and Pigments 2017; 145: 239-245.
doi: 10.1016/j.dyepig.2017.06.004
12. Günsel A, Beylik S, Bilgiçli AT, Atmaca GY, Erdoğmuş A. Peripherally and non-peripherally tetra-HBME (4-
hydroxybenzyl methyl ether) substituted metal-free and zinc(II) phthalocyanines: synthesis, characterization, and
investigation of photophysical and photochemical properties. Inorganica Chimica Acta 2018; 477: 199-205. doi:
10.1016/j.ica.2018.03.026
13. Gök HZ. Synthesis of metal-free and metallophthalocyanines containing 18- and 21-membered macrocycles with
mixed donor atoms and their metal-ion binding properties. Turkish Journal of Chemistry 2015; 39: 750-763. doi:
10.3906/kim-1501-54
14. Gök HZ, Kantekin H, Gök Y, Herman G. The synthesis and characterization of new metal-free and metalloph-
thalocyanines containing four 27-membered diazaheptathia macrocycles. Dyes and Pigments 2007; 75: 606-611.
doi: 10.1016/j.dyepig.2006.07.008
15. Brewis M, Clarkson GJ, Humberstone P, Makhseed S, McKeown NB. The synthesis of some phthalocyanines and
napthalocyanines derived from sterically hindered phenols. Chemistry European Journal 1998; 4 (9): 1633-1640.
doi: 10.1002/(SICI)1521-3765(19980904)4:9<1633::AID-CHEM1633>3.0.CO;2-O
1027

GÖK and YILMAZ/Turk J Chem
16. Gök HZ, Kantekin H, Gök Y, Herman G. The synthesis and characterization of novel metal-free and metalloph-
thalocyanines bearing four 27-membered dioxadiazapentathia macrocycles. Dyes and Pigments 2007; 75: 699-705.
doi: 10.1016/j.dyepig.2006.05.002
17. Tillo A, Stolarska M, Kryjewski M, Popenda L, Sobotta L et al. Phthalocyanines with bulky substituents at
non-peripheral positions: synthesis and physico-chemical properties. Dyes and Pigments 2016; 127: 110-115. doi:
10.1016/j.dyepig.2015.12.017
18. Gök Y, Gök HZ, Yılmaz MK, Farsak M, Karayiğit IU. Novel peripherally and non-peripherally hydrobenzoin
substituted optically active phthalocyanines: synthesis, characterization, aggregation, electrochemical properties
and catalytic applications. Polyhedron 2018; 153: 128-138. doi: 10.1016/j.poly.2018.06.053
19. Rosini C, Scamuzzi S, Uccello-Barretta G, Salvadori P. Synthesis and stereochemical characterization of some opti-
cally active 1,2-dinaphthylethane-1,2-diol. Journal of Organic Chemistry 1994; 59: 7395-7400. doi: 10.1021/jo00103a035
20. Young JG, Onyebuagu W. Synthesis and characterization of di-disubstituted phthalocyanines. Journal of Organic
Chemistry 1990; 55: 2155-2159. doi: 10.1021/jo00294a03
21. Perrin DD, Armarego WFL. Purification of Laboratory Chemicals. 2nd ed. Oxford, UK: Pergamon, 1989.
22. Sen SP, Yildiz SZ. The investigation of oxidative bleaching performance of peripherally Schiff base substituted tri-
nuclear cobalt-phthalocyanine complexes. Inorganica Chimica Acta 2017; 462: 30-39. doi: 10.1016/j.ica.2017.02.030
23. Takahashi K, Kawashima M, Tomita Y, Itoh M. Synthesis and spectral and electrochemical properties of 2,3,9,10,
16,17,23,24-octabutylthiophthalocyaninatozinc(II). Inorganica Chimica Acta 1995; 232: 69-73. doi: 10.1016/0020-
1693(94)04385-9
24. Tian M, Wada T, Sasabe H. Syntheses of new unsymmetrically dodecakis(trifluoroethoxy)-substituted metal-
lophthalocyanines by a palladium-catalayzed cross-coupling reaction. Journal of Heterocyclic Chemistry 2000; 37:
1193-1202. doi: 10.1002/jhet.5570370528
25. Moeno S, Nyokong T. Solvent and central metal effects on the photophysical and photochemical properties of
peripherally tetra mercaptopyridine substituted metallophthalocyanines. Journal of Photochemistry and Photobi-
ology A 2009; 203: 204-210. doi: 10.1016/j.jphotochem.2009.01.021
26. Ogunbayo T, Nyokong T. Synthesis and Pd(II) binding studies of octasubstituted alkyl thio derivatised phthalo-
cyanines. Polyhedron 2009; 28: 2710-2718. doi: 10.1016/j.poly.2009.05.026
27. Engelkamp H, Nolte RJM. Molecular materials based on crown ether functionalized phthalocyanines, Journal of
Porphyrins and Phthalocyanines. 2000; 4: 454-459. doi: 10.1002/1099-1409(200008)4:5<454::AID-JPP261>3.0.CO;
2-D
28. Yanık H, Aydın D, Durmuş M, Ahsen V. Peripheral and non-peripheral tetrasubstituted aluminium, gallium and
indium phthalocyanines: synthesis, photophysics and photochemistry. Journal of Photochemistry and Photobiology
A 2009; 206: 18-26. doi: 10.1016/j.jphotochem.2009.05.005
29. Kurt Ö, Özçeşmeci İ, Koca A, Gül A, Koçak MB. Synthesis, photophysical and electrochemical properties of
novel hexadeca-substituted phthalocyanines bearing naphthoxy groups. Dyes and Pigments 2017; 137: 236-243.
doi: 10.1016/j.dyepig.2016.10.014
30. Çakır V, Saka ET, Bıyıklıoglu Z, Kantekin H. Highly selective oxidation of benzyl alcohol catalyzed by new
peripherally tetra-substituted Fe(II) and Co(II) phthalocyanines. Synthetic Metals 2014; 197: 233-239. doi: 10.1016/
j.synthmet.2014.09.022
31. Saka ET, Bıyıklıoglu Z, Kantekin H, Kani I. Synthesis, characterization and catalytic activity of peripherally
tetra-substituted Co (II) phthalocyanines for cyclohexene oxidation. Applied Organometallic Chemistry 2013; 27:
59-67. doi: 10.1002/aoc.2939
1028

GÖK and YILMAZ/Turk J Chem
32. Acar I, Bayrak R, Saka ET, Biyiklioglu Z, Kantekin H. Novel metal-free, metallophthalocyanines and their
quaternized derivatives: synthesis, spectroscopic characterization and catalytic activity of cobalt phthalocyanine
in 4-nitrophenol oxidation. Polyhedron 2013; 50: 345-353. doi: 10.1016/j.poly.2012.11.032
33. Saka ET, Acar I, Biyiklioglu Z, Kantekin H. Synthesis and characterization of peripheral and non-peripheral
substituted Co (II) phthalocyanines and their catalytic activity in styrene oxidation. Synthetic Metals 2013; 169:
12-17. doi: 10.1016/j.synthmet.2013.02.029
34. Gökce S, Saka ET, Biyıklioglu Z, Kantekin H. Synthesis, characterization of metal-free, metallophthalocyanines
and catalytic activity of cobalt phthalocyanine in cyclohexene oxidation. Synthetic Materials 2013; 176: 108-115.
doi: 10.1016/j.synthmet.2013.05.028
35. Aktas S, Saka ET, Biyıklioglu Z, Acar I, Kantekin H. Investigation of catalytic activity of new Co (II) phthalo-
cyanine complexes in cyclohexene oxidation using different type of oxidants. Journal of Organometallic Chemistry
2013; 745-746: 18-24. doi: 10.1016/j.jorganchem.2013.07.013
36. Saka ET, Biyiklioglu Z. Co(II) and Fe(II) phthalocyanines: synthesis, characterization and catalytic activity on
cyclohexene oxidation with different oxygen source. Journal of Organometallic Chemistry 2013; 745-746: 50-56.
doi: 10.1016/j.jorganchem.2013.07.018
37. Özer M, Yılmaz F, Erer H, Kani İ, Bekaroğlu Ö. Synthesis, characterization and catalytic activity of novel
Co(II) and Pd(II)-perfluoroalkylphthalocyanine in fluorous biphasic system; benzyl alcohol oxidation. Applied
Organometallic Chemistry 2009; 23: 55-61. doi: 10.1002/aoc.1471
38. Kamiloğlu AA, Acar İ, Biyiklioğlu Z, Saka ET. Peripherally tetra-{2-(2,3,5,6-tetrafluorophenoxy)ethoxy} substi-
tuted cobalt(II), iron(II) metallophthalocyanines: synthesis and their electrochemical, catalytic activity studies.
Journal of Organometallic Chemistry 2017; 828: 59-67. doi: 10.1016/j.jorganchem.2016.11.022
39. Kasuga K, Tsuboi K, Handa M, Sugimori T, Sogabe K. Oxygen-oxygenation of cyclohexene catalyzed by man-
ganese(III), iron(III) and cobalt(II) complexes of tetra-tert-butylphthalocyanine in the presence of iso-butyraldehyde.
Inorganic Chemistry Communications 1999; 2: 507-509. doi: 10.1016/S1387-7003(99)00135-5
1029

SUPPLEMENTARY INFORMATION
Peripherally 1,2-dinaphthyl ethanediol substituted phthalocyanine
complexes: Synthesis, characterization, aggregation and
application in benzyl alcohol oxidation at room temperature
Halil Zeki Gök1*, Mustafa Kemal Yılmaz 2
1
Department of Biomedical Engineering, Bucak Faculty of Technology, Mehmet Akif Ersoy University,
Bucak/Burdur, Turkey.
2
Department of Chemistry, Faculty of Arts and Sciences, Mersin University, Mersin, Turkey
*Correspondence: halilzekigok@gmail.com
1

2931,07cm-1; 250,67%T
637,51cm-1; 241,98%T
861,25cm-1; 236,43%T
1712,01cm-1; 218,07%T
3049,31cm-1; 213,82%T
1422,37cm-1; 218,57%T
735,42cm-1; 208,25%T
2230,68cm-1; 188,03%T
NC
NC
1168,62cm-1; 175,42%T
990,46cm-1; 168,58%T
1041,23cm-1; 169,25%T
1092,48cm-1; 158,56%T
O
OH
1561,64cm-1; 161,32%T
1294,50cm-1; 136,46%T
1490,66cm-1; 137,54%T
778,25cm-1; 85,51%T
3416,47cm-1; 82,64%T
3473,35cm-1; 89,00%T
1596,22cm-1; 90,32%T
1249,00cm-1; 87,31%T
4000
3500
3000
2500
2000
1500
1000
600
cm-1
Name
Description
Supplementary Figure 1. FT-IR spectrum of (2)
2

NC
NC
O
OH
Supplementary Figure 2. 1H-NMR spectrum of (2)
3

NC
NC
O
OH
Supplementary Figure 3. 13C-NMR (APT) spectrum of (2)
4

NC
NC
O
OH
Supplementary Figure 4. LC-MS/MS spectrum of (2)
5

86
86
84
82
80
78
76
74
72
70
68
66
64
62
60
58
3557,7
3381,68cm-1; 77,49%T
2922,57cm-1; 76,56%T
3030,64cm-1; 74,96%T
836,12cm-1; 74,82%T
1335,22cm-1; 73,42%T
1279,76cm-1; 72,02%T
763,46cm-1; 73,64%T
696,23cm-1; 71,52%T
738,04cm-1; 70,38%T
1395,93cm-1; 69,14%T
1008,66cm-1; 68,10%T
1611,74cm-1; 65,40%T
1050,35cm-1; 64,43%T
1090,76cm-1; 62,42%T
1223,64cm-1; 58,70%T
1484,93cm-1; 55,67%T
56
55
4000
3500
3000
2500
2000
1500
1000
600
cm-1
Name
Description
Supplementary Figure 5. FT-IR spectrum of (3)
6

Supplementary Figure 6. 1H-NMR spectrum of (3)
7

Supplementary Figure 7. MALDI-TOF spectrum of (3)

93
92
90
88
86
84
82
80
78
76
74
72
70
68
2901,9
3553,4
3415,99cm-1; 85,97%T
3059,1
595,24cm-1; 84,67%T
3030,69cm-1; 84,28%T
1520,66cm-1; 78,50%T
835,64cm-1; 76,58%T
1276,04cm-1; 75,48%T
1342,91cm-1; 75,48%T
1006,30cm-1; 73,14%T
755,08cm-1; 72,22%T
696,17cm-1; 72,35%T
1407,76cm-1; 72,06%T
1066,18cm-1; 71,07%T
1610,04cm-1; 69,97%T
1230,28cm-1; 65,55%T
1098,26cm-1; 65,29%T
66
65
1482,36cm-1; 65,28%T
4000
3500
3000
2500
2000
1500
1000
500450
cm-1
Name
Description
Supplementary Figure 8. FT-IR spectrum of (4)
8

Supplementary Figure 9. MALDI-TOF spectrum of (4)
9

2,5
2
ZnPc (3) in THF
1,5
1
2E-6M
4E-6M
8E-6M
10E-6M
0,5
0
300
400
500
600
700
800
Wavelenght (nm)
2,4
2
CoPc (4) in THF
1,6
1,2
0,8
0,4
0
2E-6M
4E-6M
8E-6M
10E-6M
300
400
500
600
700
800
Wavelenght (nm)
Supplementary Figure 10. Aggregation properties of phthalocyanine complexes (3) and (4)
in THF at different concentrations (Concentration: 2×10-6, 4×10-6, 8×10-6, 10×10-6 M). Inset:
Beer-Lambert plot.
10

1,2
0,8
0,4
0
Acetonitrile
Toluene
300
400
500
600
700
800
Wavelenght (nm)
Supplementary Figure 11. UV–vis spectra of cobalt(II) phthalocyanine (4) in acetonitrile
and toluene.
11

Supplementary Figure 12. GC chromatogram of Table 1 entry 1
Supplementary Figure 13. GC chromatogram of Table 1 entry 2
12

Supplementary Figure 14. GC chromatogram of Table 1 entry 3
Supplementary Figure 15. GC chromatogram of Table 1 entry 4
13

Supplementary Figure 16. GC chromatogram of Table 1 entry 5
Supplementary Figure 17. GC chromatogram of Table 1 entry 6
14

Supplementary Figure 18. GC chromatogram of Table 1 entry 7
Supplementary Figure 19. GC chromatogram of Table 1 entry 8, Table 2 entry 2 and Table
3 entry 2
15

Supplementary Figure 20. GC chromatogram of Table 2 entry 1
Supplementary Figure 21. GC chromatogram of Table 2 entry 3
16