Novel Co(II) phthalocyanines of extended periphery and their water-soluble derivatives. Synthesis, spectral properties and catalytic activity

Article abstract of DOI:10.1016/j.molstruc.2017.07.086

Novel complexes of cobalt and copper with substituted phthalocyanines were synthesized and characterized. Their water-soluble derivatives were obtained by sulfonation under mild conditions and structurally proved. Aggregation equilibrium in water mediums was shown and influence of geometrical and electron parameters of macroheterocycle peripheral substituents on these processes was established. Catalytic activity upon liquid-phase oxidation of N,N-diethylcarbamodithiolate to thiuram E was studied. Kinetic parameters of substrate oxidation in presence of cobalt phthalocyanines were considered.

Full text of DOI:10.1016/j.molstruc.2017.07.086

Accepted Manuscript
Novel Co(II) phthalocyanines of extended periphery and their water-soluble
derivatives. Synthesis, spectral properties and catalytic activity
Anna Filippova, Artur Vashurin, Serafima Znoyko, Ilya Kuzmin, Mikhail Razumov,
Alena Chernova, Gennady Shaposhnikov, Oscar Koifman
PII:
S0022-2860(17)31031-1
10.1016/j.molstruc.2017.07.086
MOLSTR 24113
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Revised Date:
Accepted Date:
10 April 2017
24 July 2017
26 July 2017
Please cite this article as: Anna Filippova, Artur Vashurin, Serafima Znoyko, Ilya Kuzmin, Mikhail
Razumov, Alena Chernova, Gennady Shaposhnikov, Oscar Koifman, Novel Co(II) phthalocyanines
of extended periphery and their water-soluble derivatives. Synthesis, spectral properties and
catalytic activity, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.07.086
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ACCEPTED MANUSCRIPT
Novel Co(II) phthalocyanines of extended periphery and their water-soluble
derivatives. Synthesis, spectral properties and catalytic activity
a
a,b*
a
a
Anna Filippova , Artur Vashurin , Serafima Znoyko , Ilya Kuzmin , Mikhail
a
a
a
a
Razumov , Alena Chernova , Gennady Shaposhnikov , Oscar Koifman
aIvanovo State University of Chemistry and Technology, Russian Federation,
Ivanovo, 153037
bKazan Federal University, Russian Federation, Kazan, 420008
*
Corresponding author.
E-mail address: asvashurin@mail.ru
Key words cobalt phthalocyaninate, synthesis, substituent’s, solution, aggregation,
catalyst
Novel complexes of cobalt and copper with substituted phthalocyanines were
synthesized and characterized. Their water-soluble derivatives were obtained by
sulfonation under mild conditions and structurally proved. Aggregation
equilibrium in water mediums was shown and influence of geometrical and
electron parameters of macroheterocycle peripheral substituents on these processes
was established. Catalytic activity upon liquid-phase oxidation of N,N-
diethylcarbamodithiolate to thiuram E was studied. Kinetic parameters of substrate
oxidation in presence of cobalt phthalocyanines were considered.

ACCEPTED MANUSCRIPT
1
. Introduction
Metal phthalocyanines exhibit prospective chemical and photophysical
properties as individual compounds and parts of composites or hybrid materials [1-
3
9
], high catalytic activity upon redox processes [4-6]. Oxidation of mercaptans [7-
] and olefins [10-11] are of special attention. One more prospective direction of
metal phthalocyanines application is sensorics [12-13]. Development of
phthalocyanine macrocycle structure via introduction of substituents into
peripheral and non-peripheral positions allows reaching of fine tuning their
physical and chemical properties.
The important property of phthalocyanine compounds is their solubility
determining many fields of their application. Not substituted phthalocyanines have
almost no solubility in common organic solvents. Introduction of substituents into
peripheral and non-peripheral positions of phthalocyanine macrocycle forms
additional solvation centers and impart the solubility [14-16]. Obtainment of
phthalocyanines soluble in water mediums is important from the point of green
chemistry processes and technology. Introduction of sulfo- or carbon acid
fragments into annulated benzene rings of phthalocyanine macrocycle provides
phthalocyanines soluble in water mediums obtainment. Here the question of
regulation and sometimes suppression of metallophthalocyanines self-aggregation
appears. Combination of various functional groups as parts of phthalocyanine
macrocycle is a key to physical and chemical of phthalocyanine compounds [15].
Synthesis of cobalt and copper complexes of bifunctionally- and
symmetrically substituted phthalocyanines and their analogues is presented in the
work. Catalytic activity upon liquid-phase oxidation of sodium N,N-
diethylcarbamodithiolate under mild conditions is studied for water-soluble cobalt
complexes in order to find out interrelationship between terminal fragment
structure of phthalocyanines and their catalytic activity.

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2
. Experimental
2
.1. Reagents
Solvents used in the work N,N-dimethylformamide (DMF), 2-propanol,
acetone, chloroform were purified and stored in accordance to recommendations
17]. Inorganic salts applied for synthesis were previously recrystallized by
[
methods recommended in [18]. Deuterated solvents, 4-(1-methyl-1-
phenylethyl)phenole and 4-bromine-5-nitrophthalonitrile were purchased from
Aldrich. Sodium N,N-diethylcarbamodithioate (DTC) (99%, ChemMed Synthesis,
Russia) was used without additional purification.
2
.2. Equipment
Elemental analysis has been carried out by means of chromatographic
analyzer Flash HCNS-OEA 1112 (Germany). The flow rates of helium and oxygen
were 140 mL/min and 250 mL/min, respectively; the temperature of the reactor
was 1173 K, oxygen was supplied into the reactor for 250 mL/min with 12 sec
time delay.
FT-IR spectra were recorded using IR-Fourier spectrophotometer Avatar 360
-1
(
USA) in 400- 4000 cm frequency range.
NMR spectra of the solutions were recorded by means of NMR spectrometer
1
Bruker AVANCE-500 (Germany) at operating frequency 500 MHz ( H) and 100
1
3
MHz ( C). Measurements were performed under the Fourier transformation
conditions in 5 mm cells at various temperatures. Chemical shifts were measured
with reference to the internal standard – tetramethylsilane. The accuracy of
measurements was ± 0.005 ppm.
Electron absorption spectra (UV-vis) were registered by means of Unico
2
800 (USA) spectrophotometer in a spectral range of 200 – 1000 nm. Quarts

ACCEPTED MANUSCRIPT
optical cell were used for the measurements. UV-vis spectra were recorded at
2
98.15 ± 0.03 K.
Mass spectra were measured on an Axima MALDI-TOF mass-spectrometer
Shimadzu, Japan).
(
2
2
.3. Synthesis
.3.1. 4-[4-(1-methyl-1-phenylethyl)phenoxy]-5-nitrophthalonitrile (2):
2
.52 g (1 mmol) of 4-bromine-5-nitrophthalonitrile (1) and 2.12 g (1 mmol)
of 4-(1-methyl-1-phenylethyl)phenol were dissolved in 30 mL of DMF. Solution
of 1.19 g (1 mmol) of K CO in 5 mL of water was added to the mixture, next it
2
3
was stirred under 25 ºС for 30 minutes. Precipitate obtained was filtered off by
means of paper filter, washed with 2-propanol, then with water till absence of 2-
propanol and dried on air under 70-80 ºС. Yield is 3.15 g (91%). Elemental
analysis (%): calcd. for С H N O С 72.05; H 4.47; N 10.96 found С 71.95; H
2
3
17
3
3
+
5
.00; N 10.74. MALDI-TOF m/z: calcd. 383.41 found 383.22 [M] . IR (KBr) (v,
-1
cm ): 2922 and 2850 (-СН ); 2237 (-CN); 1527 (as. -NO ); 1341 (s. -NO ); 1210
3
2
2
1
(
Ar-O-Ar). Н NMR (500 MHz, CDCl ) (δ, ppm) 8.33 (s, Н1, 1Н); 7.87 (d, Н2,
3
1
Н); 7.05 (m, Н3,4, 4Н); 7.12 (m, Н5-7, 5Н); 1.76 (s, СН , 6Н).
3
2
.3.2. 4,5-di[4-(1-methyl-1-phenylethyl)phenoxy]phthalonitrile (3).
2
.52 g (1 mmol) of 4-bromine-5-nitrophthalonitrile (1) and 4.24 g (2 mmol) of 4-
(1-methyl-1-phenylethyl)phenol were dissolved in 70 mL of DMF. Solution of
2
.76 g (2 mmol) of K CO in 10 mL of water was added to the mixture, next it was
2
3
stirred under 80-90 ºС for 8 hours. Yield is 2.40 g (44 %) m.p. = 123-125 °C.
Elemental analysis (%): calcd. for С H N O C 83.19; H 5.88; N 4.96 found С
3
8
32
2
2
8
2.95; H 6.02; N 5.11. MALDI-TOF m/z: calcd. 548.68 found 549.19 [M+Н]+
+
-1
(
34.95%); 588.13 [M+K] (83.23%). IR (KBr) (v, cm ): 2967, 2929 and 2869
1
(
СН ); 2231 (CN); 1589 (γ С-С); 1318 and 1162 (δ С -H); 1211 (Ar-O-Ar). Н
3
Ar

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NMR (500 MHz, CDCl ), (δ, ppm): 7.33 (s, Н1, 2Н); 7.01-7.03 (m, Н2, 4Н); 6.96-
3
6
.98 (m, Н3, 4Н); 7.09-7.17 (m, Н4-6, 10Н); 2.19 (s, СН , 12Н).
3
2
.3.3. tetra-4-[4-(1-methyl-1-phenylethyl)phenoxy]tetra-5-nitrophthalocianinates
of cobalt and copper (1a, 1b).
Thoroughly grounded mixture of 0.38 g (0.1 mmol) of 4-[4-(1-methyl-1-
phenylethyl)phenoxy]-5-nitrophthalonitirle (2), 0.05 g (0.8 mmol) of urea and 0.57
g (0.2 mmol) of CоСl ×6H O was heated under 200 ºС for 2 hours. Reaction
2
2
mixture after process is finished was washed with diluted hydrochloric acid to
remove urea destruction products, then with water till absence of reaction on
chloride-anions with silver nitrate, next it was dried on air under 70-80 ºС,
dissolved in chloroform and exposed column chromatography on aluminum oxide
eluting with chloroform. Obtained solid of dark-green color insoluble in water is
well soluble in chloroform and DMF. Copper complexes were obtained by similar
method using copper chloride.
1
6
1
a: Yield is 0.33 g. (92 %). Elemental analysis (%): calcd. for С H CoN O С
9
2
68
12 12
9.39; H 4.30; N 10.55 found С 69.21; H 4.11; N 10.42. MALDI -TOF m/z: calcd.
+
-1
591.44 found 1591.89 [M] . IR (KBr) (v, cm ): 2953, 2935 and 2850 (СН ); 1538
3
(
as NO ); 1352 (s NO ); 1242 (Ar-O-Ar).
2
2
1
6
1
b: Yield is 0.35 g. (87 %). Elemental analysis (%): calcd. for С H CuN O С
9
2
68
12 12
9.19; H 4.29; N 10.52 found С 69.00; H 4.56; N 10.20. MALDI-TOF m/z: calcd.
+
-1
597.17 found 1597.82 [M] . IR (KBr) (v, cm ): 2964, 2923 and 2850 (СН ); 1538
3
1
(
as NO ); 1346 (s NO ); 1209 (Ar-O-Ar). Н NMR (500 MHz, CDCl ), (δ, ppm):
2
2
3
8
1
.33 (s, Н1, 4Н); 7.43 (m, Н2, 4Н); 7.17 (m, Н5, 6, 7, 24Н); 7.05 (m, Н3, 4, 16Н);
.75 (s, СН , 24Н).
3
octa-4,5-[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyaninate of cobalt and
copper (2a, 2b).
Thoroughly grounded mixture of 55 mg (0.1 mmol) of the compound (5), 50
mg (0.8 mmol) of urea and 23.8 mg (0.1 mmol) of CоСl ×6H O was heated under
2
2

ACCEPTED MANUSCRIPT
1
55-160 ºС for 1.5 hours. Reaction mixture after process is finished was dissolved
in chloroform and exposed column chromatography on aluminum oxide eluting
with chloroform. Obtained solid of dark-green color insoluble in water is well
soluble in chloroform, acetone and DMF. Copper complexes were obtained by
similar method using copper chloride.
2
8
2
1
2
8
2
1
a: Yield is 42.5 mg (78%). Elemental analysis (%): calcd. for С H CоN O С
1
52 128
8
8
1.01; H 5.72; N 4.97 found С 80.82; H 6.00; N 4.82. MALDI-TOF m/z: calcd.
+
-1
251.13 found 2252.63 [M+Н] . IR (KBr) (v, cm ): 2954, 2923 and 2862 (СН );
3
561 (γ С-С); 1328 and 1125 (δ С -H); 1213 (Ar-O-Ar).
Ar
b: Yield is 43.8 mg (80%). Elemental analysis (%): calcd. for С H CuN O С
1
52 128
8
8
0.84; H 5.71; N 4.96 found С 80.22; H 5.95; N 4.90. MALDI-TOF m/z: calcd.
+
-1
255.91 found 2257.57 [M+2Н] . IR (KBr) (v, cm ): 2966, 2929 and 2872 (СН );
3
1
602 (γ С-С); 1272 and 1137 (δ СAr-H); 1207 (Ar-O-Ar). Н NMR (500 MHz,
CDCl ), (δ, ppm): 7.33 (s, Н1, 8Н); 7.01-7.03 (m, Н2, 16Н); 6.96-6.98 (m, Н3,
3
1
6Н); 7.07-7.22 (m, Н4-6, 40Н); 2.17 (s, C-Н , 48Н).
3
2
.3.4.
tetra-4-{4-[1-methyl-1-(4-sulfophenyl)ethyl]phenoxy}tetra-5-
nitrophthalocyaninate of cobalt (1с).
Tetra-5-[4-(1-methyl-1-phenylethyl)phenoxy]tetra-4-nitrophthalocyanine of
cobalt (1a) (160 mg, 0.01 mmol) was combined with mixture of 2 mL (18 mmol)
of chlorsulfonic acid and 2 mL (18 mmol) of thionilchloride under room
temperature for 2 hours [19]. The reaction mixture was poured onto ice treated
with sodium chloride after the stirring is finished. Formed precipitate was collected
by means of Shotts filter, dried in exicator over sulfuric acid for 3 days. Obtained
sulfochloride was extracted with acetone, the solvent was distilled off. The mixture
next was boiled with water till entire dissolving. The solvent then was distilled off.
Final purification was performed via column chromatography: eluent – DMF,
sorbent – silica gel M 60. Obtained products are solid compounds of dark-green
color soluble in water, ammonia solution water-alkali solutions, DMF. Yield is 137
mg (72%). Elemental analysis (%): calcd. for C H CoN O S C 57.77; N 8.79;
9
2
68
12 24 4

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H 3.58; S 6.70 found C 57.71; N 8.56; H 3.96; S 6.38. IR (KBr) (v, cm ): 2919,
-1
2
852 (CH ); 1504 (as NO ); 1340 (as NO ); 1174 (S=O); 1020 (С-S).
3
2
2
2
.3.5. octa-4,5-{4-[1-methyl-1-(4-sulfophenyl)ethyl]phenoxy}-phthalocyanine (2с)
Into double-necked flask 2 mL of thionylchloride and 2 mL of chlorsulfonic
acid were loaded, then 226 mg (0.01 mmol) of cobalt octa-4,5-[4-(1-methyl-1-
phenylethyl)phenoxy]phthalocyaninate (2a) was added. The mixture was stirred
under 20-25 °С for 2 hours. The reaction mixture was poured onto ice treated with
sodium chloride after the stirring is finished. Formed precipitate was collected by
means of Shotts filter, dried in exicator over sulfuric acid for 3 days till complete
drying and absence of thionylchloride odor. Desired compound was extracted with
acetone. The extract was filtered off by means of paper filter, moved to porcelain
beaker and solvent was removed. Aqueous DMF (75-80%) was added to obtained
solution, solvent was distilled off on water bath without boiling. The mixture after
process finish was dissolved in DMF and exposed to column chromatography on
silica gel M60 eluting with DMF. Yield is 273 mg (94%). Elemental analysis (%):
calcd. for C H CoN O S C 63.08; H 4.46; N 3.87 found C 62.72; H 4.82; N
1
52 128
8
32 8
+
-1
3
2
.56. MALDI-TOF m/z: calcd. 2891.57 found 2891.84 [M] . IR (KBr) (v, cm ):
921 (СН ); 1238 (Ar-O-Ar); 1122 (S=O); 1039 (C-S).
3
2
.4. Spectral studies
Spectral researches were carried out for isomolar series of solutions.
Calculation of stability constant for molecular complex of metal phthalocyanine
with DMF formation was carried out based on changes of absorption density of
solution in range of Q-band. Equilibrium concentration of molecular complex was
calculated as:


A0  A


0
c
cCoPcDMF  c

CoPc
(1)
A0  A

ACCEPTED MANUSCRIPT
where cCoPс·DMF – equilibrium concentration of molecular complex, c0CoPс
–
initial concentration of macrocycle. A , A and A – initial, equilibrium and final
0
c
∞
values of solution’s optical density of Q-band respectively.
Concentration of free ligand was determined according to equation:


A0  A
c


0
0
cDMF  c
 c

DMF
CoPc
(2)
A0  A
Taking into account equations 1 and 2 the formula for calculation of stability
constant will be:


A0  Ac

/

Ac  A




K 
s
(3)
0
0

c
 c


A0  Ac

/

A0  A


DMF
CoPc


The investigation was carried out with excess of ligand relative to the
metallophthalocyanine. That is why equilibrium concentration of DMF is
considered to be equal to its initial concentration. It simplified the process of
calculating of Ks:
A0  Ac
K 
s
0
(4)
(
A  A )c
0

DMF
To estimate the number of units of forming sandwich associates the semi-log
method of Bent-French by value of the slope of plots was applied:



A  A 
0
c
lg
 f (lgcL )
(5)


Ac  A

where c – equilibrium concentration of axial ligand, A , A и A – initial,
L
0
c
∞
equilibrium and final values of solution’s optical density respectively.
Dimerization constants were calculated based on spectral data according to
known method [20]. Equation (6) was used.
2

M 

D
2
Kdim

(6)
i
2

i D

c
CoPc

ACCEPTED MANUSCRIPT
here ε – CoPc monomer extinction, ε – CoPc dimer extinction, ε – extinction of
M
D
i
i
investigated CoPc solution, c – current concentration of CoPc.
2
.5. Studies of catalytic activity
The catalytic activity of metallophthalocyanines was tested with a known
21-22] reaction of sodium N,N-diethylcarbamodithioate (DTC) oxidation. It
proceeds according to general scheme 1.
[
C H
S
C2H5
S
S
S
S
C2H5
C2H5
2
5
cat
2
N
C
+ 1/2 O + H O
N
C
C
N
+
2 NaOH
2
2
C H
SNa
C2H5
2
5
Scheme 1. Scheme of disulfide formation.
Advantages of this reaction are low toxicity of initial materials and
possibility of monitoring of concentration of initial and desired materials and
identification of reaction products using electron absorption (UV-vis spectra) and
FT-IR spectroscopy methods. Experiments to study the kinetics of DTC oxidation
were carried out in thermostatic cell in which the solution of DTC of 650 mL was
loaded.
The air needed for oxidation was fed via micro compressor with constant
rate of 2 L/min. The reaction takes place in kinetic region under these parameters
[23]. After establishing a constant temperature of reaction mixture, it was stirred
and sample of 2 mL was taken to determine initial concentration of DTC, then
compressor was turned on. This moment was taken as the beginning of the
reaction. Samples of 2 mL were taken periodically during the experiment to
determine current concentration of DTC. The concentration of DTC was monitored
by spectrophotometric method.
Under conditions of constant concentrations of oxygen and catalyst, constant
pH of solution the rate of DTC oxidation is described by first order kinetic
equation:

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

c

k c
(7)
obs DTC
t
-1
where k – observed constant of the rate, s .
obs
It is confirmed by straightness of graphics in coordinates lnc − t and
constancy of rate constants calculated according to the equation:
c0
ln c
k 
(8)
obs
t
where с – initial concentration of DTC, c – current (t) concentration of
0
DTC.
The rate constants of (n + 1)-order were calculated using Eq. (9).
k
2
w
98
obs
i
k 
(9)
c
DTC

The activation energy (Е ) for the studied temperature range was calculated
by the Arrhenius equation in the integrated form:



TT  k

1
2
2
E 19.1
lg


(10)
T2 T
1
k1
where T and T —temperatures and k and k - observed rate constants at
1
2
2
1
current temperatures.

Entropy change for the formation of transition state S was calculated with
eq (11):

E

298
w

S 19.1lnk

 253
(11)
2
98
Degree of transformation was calculated according to eq. (12):
χ = (c c )/c
(12)
0
- τ
0
where с – initial concentration of DTC, c – current concentration of DTC.
0
τ
1
Disulfide formation was monitored with FT-IR spectra, and H NMR, and
1
3
1
C NMR. H NMR of DTC oxidation (500 MHz, D O), (δ, ppm): 4.32 (m, J = 15
2
1
3
Hz, 4H, CH ); 1.39 (t, J = 5 Hz, 6H, CH ). C NMR of DTC oxidation (100 MHz):
2
3
-1
1
1.65; 27.50; 49.11; 205.02. IR of DTC oxidation IR (KBr), (v, cm ) 2979 (as

ACCEPTED MANUSCRIPT
CH ); 2847 (as CH ); 1476 (δ CH ); 1378 (st C-N); 1269 (st C=S); 1075 (d C-S).
3
2
2
During oxidation of DTC the formation of diethylcarbamothioylsulfanyl-N,N-
1
diethylcarbamodithioate (Thiuram E) is observed. H NMR of Thiuram E obtained
by DTC oxidation (500 MHz, CDCl ), (δ, ppm): 3.71-3.77 (m, 8H, CH ); 1.29-
3
2
1
3
1
.23 (m, 12H, CH ). C NMR of Thiuram E obtained by DTC oxidation (100
3
MHz): 10.49; 25.72; 52.04; 51.26; 190.05. IR of Thiuram E obtained by DTC
-1
oxidation IR (KBr): (v, cm ): 2975 (as CH ); 2861 (as CH ); 1505 (δ CH ); 1380
3
2
2
(st C-N); 1273 (st C=S); 1143 and 995 (-S-S-).
3
. Results and Discussion
3
.1. Nitriles synthesis
Synthesis of 4-[4-(1-methyl-1-phenylethyl)phenoxy]-5-nitrophthalonitrile
2) was performed according to scheme 2 using 4-bromine-5-nitrophthalonitrile (1)
(
as initial compound. Reaction was carried out in aqueous DMF solution under
temperature of 30 °С in presence of deprotonating agent (K CO ).
2
3

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H3
H4
H5
CH3
H6
H2
NC
NC
Br
NC
O
H7
OH
CH3
H5'
0
DMF/H O, 25 C, 0.5 h K CO
NO2
2
2
3
H3'
H4'
H6'
NC
NO2
1
2
H1
DMF,
85-90
0
C,
8
h
OH
K
2
CO
H2
NC
3
CH3
O
NC
CH3
O
H1
3
CH3
H3C
Scheme 2. Synthesis of nitriles.
1
Composition and structure of phthalonitrile 2 were indetified using H NMR,
IR spectroscopy, MALDI-TOF mass-spectrometry and elemental analysis data. IR
-1
spectrum of the phthalonitrile has C≡N valent vibrations band on 2234 cm ,
methyl groups of 4-(1-methyl-1-phenylethyl)phenoxygroup on 2950 and 2880 cm-
1,
NO -group symmetrical (1365-1375 cm ) and asymmetrical (1555-1565 cm )
-1
-1
2
1
vibrations [24]. H NMR spectrum of phthalonitrile 2 exhibits signals in strong
field region assumed to protons of 4-(1-methyl-1-phenylethyl)phenyl substituent
methyl groups on 1.76 ppm. There are signals in weak field region related to
protons of phthalonitrile benzene ring and oxyaril substituent. H proton signal
1
places on 8.33 ppm.

ACCEPTED MANUSCRIPT
3
2
3000
2500
2000
1500
1000
500
-1
Wavenumber, cm
Figure 1. IR spectra of nitriles 2 and 3.
Symmetrically-substitued phthalonitrile 3 was obtained starting from nitrile
under harsher conditions. In opposite to compound 2 obtained under common
1
conditions the 3 requires holding of reaction mixture under 80-90 ºС for 8 hours.
As a resulting substance viscous red-brownish liquid containing desired compound
is formed. Phthalonitrile 3 was extracted from reaction mixture by means of
separation funnel and placed to conical flask of 100 mL volume, then 10 mL of
isopropyl alcohol and water mixture (1:1) was added and mixture held for 72
hours. Initially uncolored water-alcohol layer gained intense red-brown color and
desired phthalonitrile precipitated. Obtained precipitate was filtered off, washed
with 2-propanol till colorless filtrates, then with water to remove 2-propanol and
dried in vacuum under 50 ºС.
-1
IR-spectrum of 3 indicated vibrations of nitrile-group on 2233 cm and Ar-
-1
O-Ar 1217 cm . NO – groups vibrations were not registered. There were no
2
1
separated signals for H and H protons (7.33 ppm) within H NMR spectra that
1
2
indicates equivalent environment.

ACCEPTED MANUSCRIPT
.2. Metallophthalocyanines synthesis
3
Metal complexes of phthalocyanines were obtained by template synthesis
method (Scheme 3) via melting of nitrile 2 or 3 with corresponding metal chloride.
Synthesis of symmetrically-substituted cobalt and copper phthalocyaninates (2a,
2
b) proceeds under temperatures for 40° lower comparing to synthesis of
bifunctional derivatives 1a and 1b, melting of which was under 200 °С.

ACCEPTED MANUSCRIPT
R
O
O
R
N
N
N
N
NC
O
R
0
MCl x nH O, 150-200 C
M
2
2
NC
R:
R
O
NO2
1
2
O
R
O
M: Co 1a, 2a; Cu 1b, 2b
C
0
SO H
3
20-25
Cl,
3
+
HSO
2
SOCl
R
O
SO H
O
R
3
N
N
N
M
N
R
O
SO3H
O
R
M: Co 1c, 2c; Cu 1d, 2d
SO H
3
Scheme 3. Synthesis of metallophthalocyanines.
Electron absorption spectra (UV-vis) of compounds 1a, 1b, 2a and 2b in
various solvents are specific for metal phthalocyaninates (Figure 2). Splitting of
absorption Q-band designates strong aggregation of these macrocycles due to π-
stacking. UV-vis show slight solvatochromic effect (Table 1) caused by change of
solvent solvation characteristics.

ACCEPTED MANUSCRIPT
4
0,6
3
1
0,4
2
5
0,2
0,0
500
600
700
800
900
Wavelength (nm)
Figure 2. UV-vis spectra of nitro-substituted cobalt phthalocyaninates: 1 – 1а in
DMF, 2 – 1c in DMF, 3 – 1a in H SO , 4 – 1c in H SO , 5 – 1c in H O (pH 13).
2
4
2
4
2
Water-soluble derivatives were obtained via interaction of cobalt (1a, 2a)
and copper (1b, 2b) phthalocyaninates with mixture of thionyl chloride and
chlorsulfonic acid under room temperature for 2 hours till corresponding
sulfochlorides obtainment (Scheme 2), which were transformed to sulfonic acids
via hydrolysis. Yield of sulfonated derivatives of cobalt and copper
phthalocyaninates was 78-82%.

ACCEPTED MANUSCRIPT
solvent
macrocycle
DMF
683
685
694
696
665
679
670
CHCl3
678
696
-
H O
H SO
2
2
4
1
a
-
-
797
804
787
794
823
838
797
1
b
1
c
704
690
-
1
d
-
2
a
673
684
-
2
b
-
2
c
679
Table 1. Absorption spectral data for Q-band of metallophthalocyanines (nm) in
various solvents.
Bathochromic shift of absorption Q-band is observed within solutions in
organic solvents upon transformation of metal phthalocyaninate nitro-derivatives
(1a, 1b) to their symmetrical analogues. Observed solvatochromic effect relates to
change of centers of solvent – macrocycle solvation interaction. Axial coordination
of one or two solvent molecules by central metal cation is becoming predominant
upon solvation of phthalocyanine macrocycle in DMF, herewith in case of
chloroform this fact is caused by hydrogen bond. Significant bathochromic shift of
absorption Q-band is observed within UV-vis in solutions of sulfuric acid due to
protonation of meso-position of macrocyclic fragment and the regularity has an
inverse form.
3
.3. Aggregation in water mediums
Introduction of ionogenic groups to phthalocyaninates composition imparts
them solubility in water mediums enhancing potential application ways as
environmental-friendly catalysts and photocatalysts for mercaptanes (RSH)
oxidation. Besides sulfo-group as part of metal phthalocyaninate may functionalize

ACCEPTED MANUSCRIPT
as anchoring group upon immobilization of the macrocycle on inorganic polymers,
for example on silica [25-27].
Investigation of electron absorption spectra (Figures 2 and 3) of sulfonated
metal phthalocyanines confirmed difference of aggregation for these compounds in
water and DMF solutions. In this way, bifunctional derivatives of phthalocyanine
macrocycles exhibit strong association that corresponds to diffuse electron
absorption spectrum (Figure 2). Absorption band about 630 nm is registered in
UV-vis spectrum of water and DMF solutions of 1c and 1d within concentration
-7
range up to 10 mol/L that corresponds to H-dimers according to literature data
28]. On the contrary octa-sulfonated macrocycles in these mediums are
predominantly monomeric (Figure 3). Association processes takes place upon
[
-5
macrocycle concentration is over 8×10 mol/L. Some broadening of absorption Q-
band for water solution of 2c may be explained by formation of phthalocyaninate
associates linked due to water structure. In this case there is no interaction between
macrocycles π-systems, and solvent molecules are included into aggregate cavity.
Stabilization of non-covalent associates takes place in solution for complexes 2c
and 2d in contrary to behavior of sulfonated cobalt phthalocyanines known
previously in water mediums [29]. This is possible due to interaction between
extended peripheral substituents of two macrocycles significantly distanced from
aromatic π-system.

ACCEPTED MANUSCRIPT
1
1,6
2
1,2
3
0,8
0,4
0,0
500
600
700
800
900
Wavelength (nm)
Figure 3. UV-vis spectra of cobalt phthalocyaninates solutions: 1 – 2c in H O (pH
2
1
3), 2 – 2c in DMF, 3 – 2c in H SO .
2
4
Inversion of solvatochromic effect for sulfonated metallophthalocyanine
derivatives compared to predecessors is caused by change of solvation centers on
phthalocyanine macrocycle periphery and aggregation equilibriums of the system.
High degree of sulfo-groups ionization in water-alkali mediums leads to
competing both solvent and ionized peripheral substituent of nearest macrocycle
for central metal cation accompanied with J-aggregates formation.
Aggregation degree and type of the aggregates have significant influence on
catalytic activity of these macrocycles upon liquid-phase processes. Data on
aggregation and religanding processes helps to evaluate catalytic properties more
detailed. Possibility of solvent replacement on introduced substrate in water-alkali
mediums is promising for transformation of mercaptanes to disulfides by means of
phthalocyaninate complexes, before all cobalt ones, as catalysts.
As it was shown previously, macrocycle 1c is aggregated in water-alkali
solution, electron absorption spectrum registers broad maximum of diffuse nature.

ACCEPTED MANUSCRIPT
Investigation of UV-vis concentration dependence for water-alkali solution of 1c
indicates unavailability of association equilibrium shift toward monomeric forms
due to dilution.


nCoPc
(13)
(CoPc)n

Method of mathematical decomposition of electron absorption spectrum on
the components was applied to determine contribution of monomeric and
associated 1c macrocycle forms [30-31] (Figure 4). Obtained results showed the
shift of association equilibrium toward monomers upon dilution of solution
keeping H-associates linked by interaction of peripheral substituents.
Concentration limit of aggregation beginning in water mediums for 1c is 2×10-7
mol/L.
0,080
1
0,20
0,075
2
1c
0,070
0,15
0,065
4
0,10
0,060
3
0,055
0,05
0,050
0,00
3,8
4,0
4,2
4,4
4,6
4,8
5,0
500
550
600
650
700
750
-
lgCCoPc
Wavelength (nm)
a)
b)
Figure 4. a) – decomposition of UV-vis spectra for 1c 1 – experimental data,
– calculated curve, 3 – monomer absorption, 4 – dimer absorption; b) –
2
concentration dependence of monomer-dimer equilibrium.
Accessibility of phthalocyanine macrocycle coordination unit upon catalytic
process determines efficiency and selectivity of phthalocyanines as catalysts. We
investigated the process of solvent displacement from macrocycle coordination
sphere.

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lgε
lgε
macrocycle
lgKdim
CoPc:DMF
Ks
(
Н-aggregate)
(monomer)
4.98
1
2
с
с
3.39
6.74
3.97
1:2
2:5
3.79
3.37
3.94
4.53
Table 2. Aggregation parameters of cobalt phthalocyaninate sulfonic acids.
Coordination of DMF for 1c proceeds in one stage forming stable complex
(Table 2). Complex composition determined with angle tangent from equation 5
resulted in CoPc:DMF 1:2 that indicates solvent replacement from fifth and sixth
coordination positions of metal phthalocyanine and exchange it on DMF.
2c
lgInd
0
0
0
,8
,4
,0
1
0
1
2
5
x10 M
C
DMF
0
4
8
12
lgCDMF -0,6
0,0
0,6
-
-
1
c
2
c
Figure 5. Dependence of indication ratio from ligand concentration within
specific solvation region. DMF titration curve for 2c (inserted).
Solvation interaction of 2c and introduced ligand proceeds in two steps
(Figure 2, inserted). The first one is formation of specific coordination complex of
2
:5 composition. Interaction transforms from specific to universal upon increase of
DMF concentration in water-alkali solution of 2c. This fact suggests key role of
peripheral substituents electron effects affecting conjugated macrocycle π-system

ACCEPTED MANUSCRIPT
and hence on coordination unit upon solvation of 1c. In case of symmetrically-
substituted macrocycle 2c structural effects of substituents linking ligand on the
periphery become predominant. Observed phenomena are crucial for further
interpretation of catalytic data involving metallophthalocyanines.
3
.4. Catalytic activity
Catalytic activity of 1c and 2c was tested within liquid-phase oxidation of
sodium N,N-carbamodithiolate. Mercaptans oxidation proceeds in several steps
according to scheme 4 depending on process conditions.
O
O O
RS SR
O O
[
O]
[O]
[O]
2RSH
RS-SR
RS SR
O
-
2H
Scheme. 4. Scheme of mercaptans oxidation.
Our previous researches showed substituted cobalt phthalocyanine
derivatives to have high selectivity with the termination of the reaction at the stage
of disulfide formation [32-35]. Moreover, mild reaction conditions, namely use of
air oxygen as oxidant and relatively low basicity of the medium, promote this.
Based on kinetic research [32] catalytic activity of these compounds is
determined by influence of peripheral substituents, their nature and structure on
macrocycle. This is caused by change of both peripheral substituents electron
effects and restructuring of macrocycles in solutions.
Figure 6 presents temperature dependence of DTC oxidation rate in presence
of catalysts 1c and 2c.

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4,0
3,6
1c
3,2
2,8
2,4
2c
0,00320
0,00328
0,00336
0,00344
1/T
Figure 6. Temperature dependence of DTC oxidation rate.
Equal activation parameters of DTC oxidation (Table 3) catalyzed by 1c and
c indicate similar state and nature of active centers during catalysis. Based on
2
known
data
about
mercaptans
oxidation
mechanism
involving
metallophthalocyanines [32, 36] formation of triple substrate-catalyst-oxygen
intermediate complex requires increase of system order that is reflected in negative
values of system activation entropy (Table 3). This means both aggregated form 1c
and macrocycle exciting in solution as monomers (2c) are less ordered than
monomolecular complex.
kw×103
E≠
ΔS≠
phthalocyanine
χ
L×(mol×s)-1 kJ×mol-1 J ×(mol×K)-1
1
2
с
с
21
42
2.67
2.62
-248
-247
0.86
0.75
Table 3. Kinetic parameters of DTC oxidation.
Conclusion

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Resulting from work bifunctionally- and symmetrically substituted
phthalocyanines were synthesized. Catalytic activity of the water-soluble
compounds was studied. Series of obtained phthalocyanines was found to exhibit
interrelationships between structure of the terminal fragment and catalytic
properties. Based on this, one may conclude the possibility to predict catalytic
performance of the compounds based on their structure.
Obtained results provide possibility of compensation aggregation state of
macrocycle upon catalysis by sterical effect of peripheral substituent allowing
increase of process rate without mechanism change.
Acknowledgments
The work was supported by a grant from the President of the Russian
Federation [grant number MK-161.2017.3] and partially by the RFBR [grant
number 16-53-00100].
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Highlights
Novel cobalt and copper phthalocyaninates bearing with bulky fragments on
periphery are synthesized. Their water-soluble analogues are obtained.



The compounds are fully characterized.
The compounds are prospective as catalysts.