A new water-soluble sulfonated cobalt(II) phthalocyanines: Synthesis, spectral, coordination and catalytic properties

Article abstract of DOI:10.1142/S1088424615500753

Novel complexes of cobalt(II) with sulfonated derivatives of phthalocyanines are synthesized. The influence of the sulfonated group's number in peripheral substituent on solubility of macrocycle and ability to form ordered structures in solution is showed. Transition from H-aggregates to monomeric phthalocyanine structures and sandwich-type dimers was found during formation of metallophthalocyanine complexes with 1,4-diazabicyclo[2.2.2]octane. The catalytic activity of metallophthalocyanines was studied on the model of Merox process

Full text of DOI:10.1142/S1088424615500753

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2015; 19: 1–14
DOI: 10.1142/S1088424615500753
Published at http://www.worldscinet.com/jpp/
A new water-soluble sulfonated cobalt(II) phthalocyanines:
Synthesis, spectral, coordination and catalytic properties
a◊
b
c
b◊◊
Artur Vashurin* , Anna Filippova , Serafima Znoyko , Alena Voronina ,
d
e◊◊
c
e
Olga Lefedova , Ilya Kuzmin , Vladimir Maizlish and Oscar Koifman
a
Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
b
Faculty of Fundamental and Applied Chemistry, Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
Department of Technology of Fine Organic Synthesis, Ivanovo State University of Chemistry and Technology,
c
Ivanovo 153000, Russia
d
Department of Physical and Colloid Chemistry, Ivanovo State University of Chemistry and Technology,
Ivanovo, 153000, Russia
e
Research Institute of Macroheterocycles of Ivanovo State University of Chemistry and Technology,
Ivanovo 153000, Russia
Received 22 May 2015
Accepted 5 June 2015
ABSTRACT: Novel complexes of cobalt(II) with sulfonated derivatives of phthalocyanines are
synthesized. The influence of the sulfonated group’s number in peripheral substituent on solubility of
macrocycle and ability to form ordered structures in solution is showed. Transition from H-aggregates
to monomeric phthalocyanine structures and sandwich-type dimers was found during formation
of metallophthalocyanine complexes with 1,4-diazabicyclo[2.2.2]octane. The catalytic activity of
metallophthalocyanines was studied on the model of Merox process.
KEYWORDS: sulfonated phthalocyanines, synthesis, aggregates, DABCO, catalyst, dye.
as molecular switches, fluorescent sensors, photonic
INTRODUCTION
wires, and catalysts [1–3]. MPc have a wide range of
Water soluble metallophthalocyanines (MPc) are
applications such as in medicine as photosensitizer of
unique molecules with several centers of specific
photodynamic therapy [4, 5] electronics [6], non-linear
solvation. Metal complexes of phthalocyanines have
optics [7] and as catalysts [8, 9]. These applications
unique physical and chemical properties caused by their
ability to interact with molecular and charged ligands.
arise from the MPc conjugated p-system, the ability to
coordinate various ligand in the central cavity, and their
Self-association of MPc in solutions is one of the most
chemical and physical stability. MPc can be tuned for
important native properties of such compounds. Self-
different applications by introducing various substituents
assembly is a prominent, naturally occurring phenomenon
at the different positions on the ring [10–13].
that involves the automatic formation of dimers and
Sulfonationofphthalocyaninespromotesitssolubilityin
higher aggregates of various and often complex
structures. Interest in understanding assembly processes
has grown enormously over the past decade. It is caused
by potential applications in various nanomaterials, such
waterandenhancestheprocessofMPcself-association[14,
15]. Nevertheless, precisely the tetrasulfonic acid of cobalt
phthalocyanine is widely used in Merox process [16]. Self-
association processes of cobalt tetrasulfophthalocyanine
reduce its catalytic activity [17]. Obviously, the possibility
to control the association state of water soluble MPc in
solutions gives new ways to create materials based on such
compounds. The synthesis of novel cobalt complexes of
◊
SPP full and ◊◊ student member in good standing
*
Correspondence to: Artur Vashurin, email: asvashurin@mail.ru,
tel: +7 (910)-990-9125
Copyright © 2015 World Scientific Publishing Company

2
A. VASHURIN ET AL.
phthalocyanines with extended periphery is presented in
the work. Also there was attempt to vary the associative
state of metallophthalocyanines in water mediums through
processes of axial coordination of 1,4-diazabicyclo[2.2.2]
octane (DABCO). The approach presented here is a new
route to assembly of the phthalocyanines molecules with
the assistance of non-covalent interaction in aqueous
media. The influence of association on catalytic activity of
metallophthalocyanines is showed.
calcd. C, 52.01; N, 12.64; H, 3.82; S, 5.78; that is in a
good agreement with experimental data. Hydrated form
CoTSPc1 is fairly stable and may be decomposed under
the temperature near the critical temperature of proper
phthalocyanine. Further drying of the compound was
carried out under the temperature of 380 K in vacuum
oven. The drying was stopped after reaching of constant
mass of sample.
There were vibrational bands registered in IR spectra
-
1
(
(
KBr) of CoTSPc1: n, cm 745 (C–N), 1045 (N=N), 1230
Ar–O–Ar), 1060 (C–S), 1150–1190 (S=O in SO H), 1185
3
+
RESULTS AND DISCUSSION
(O–S–O). MS (MALDI-TOF): m/z 1932.71 [M + 4H] .
1
H NMR (500 MHz, DMSO-d ): d, ppm 7.45 (Ar–5H),
6
7
.94 (Ar–4H), 8.07 (Ar–6H), 8.29 (Ar–3H) — of triazole
Synthesis of sulfonated phthalocyanines
group, 7.64 (Ar–8H), 7.73 (Ar–7H), 7.85 (Ar–11H), 8.18
(Ar–10H), 8.53 (Ar–9H), 8.85 (Ar–12H) — of naphthoxy
2
,9,16,23-Tetrakis(1-benzotriazolyl)-3,10,17,24-
tetrakis(4-sulfo-1-naphthoxy)phthalocyaninate
cobalt(II) (CoTSPc1) was obtained according to the
scheme 1.
group, 8.97 (SO H). The presence of chemical shift of
sulfonic groups protons indicates the molecular form of
macrocycle in DMSO.
3
The elemental analysis for CoTSPc1 calcd. (%):
C, 61.67; N, 14.98; H, 2.80; S, 6.86. The experiment
showed that obtained powder contains (%): C, 52.00;
N, 12.43; H, 4.05; S, 5.36. The difference of obtained
results is probably caused by the adsorbed water
contained in synthesized phthalocyanines. That is why
we recalculate the composition of metallophthalocyanine
to hydrated form containing 16 molecules of water
There is no chemical shift of sulfonic group’s proton in
1
H NMR spectra of CoTSPc1 (D O). It indicates ionized
2
form of macrocycle in solution. Besides, the position of
chemical shifts of Ar–H protons is displaced toward high
field for 0.5–5 ppm. This fact indicates high degree of
association due to p–p overlapping of two macrocycles
and peripheral interactions.
2,9,16,23-Tetrakis(1-benzotriazolyl)-3,10,17,24-
tetrakis(1,6-disulfo-2-naphthoxy)phthalocyaninate
(
4 for each peripheral substituent). For CoTSPc1 × 16H O
2
N
N
N
R
N
N
N
2
R
6
5
N
1
3
4
N
N
N
N
Co
N
N
N
N
R
N
N
N
SO H
3
R
N
N
10
8
7
CoTSPc1
or
12
O
O
SOCl2 + HSO3Cl 293 K/H2O, reflux
R:
R:
or
HO3S
9
10
8
CoTSPc2
7
HO3S
O
O
Scheme 1. Synthesis of CoTSPc1 and CoTSPc2
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 2–14

A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
3
cobalt(II) (CoTSPc2) was obtained according to
7.48 (Ar–5H), 7.75 (Ar–4H), 7.94 (Ar–6,7H), 8.14 (Ar–
3H) — of triazole group, 8.33 (Ar–2H) — macrocycle,
8.72 (Ar–8,9,11H) — of naphtoxy group, 8.83, 8.81
Scheme 1. It was found for the first time that sulfonation
of 2-naphtoxy substituted fragment of metallo-
phthalocyanine’s peripheral substituent is in positions 1
and 6. It leads to formation of octasulfonated derivative of
metallophthalocyanine. As it has been shown previously
sulfonation of 1-naphtoxy substituted fragment of
metallophthalocyanine’s substitutent is in position 4 only
and as result tetrasulfonated derivative of macrocycle is
obtained.
(SO H). There are no signals of sulfonic group’s protons
3
in D O as for CoTSPc1. It indicates the ionized form of
2
macrocycle.
Spectral properties and aggregation of CoTSPc1
and CoTSPc2
It may be caused by the difference of electronic
structures of 1- and 2-naphtoxy groups. Introduction of
sulfonic group in the first benzene ring of 1-naphtoxy
substituent deactivates second benzene ring of 1-naphtoxy
substituent. That is why the second benzene ring does
not react in electrophilic substitution. It is connected
with decrease in the electronic density on carbon atoms
of second benzene ring of naphthalene fragment. This
MPc may be monomeric and associated in solutions:

→
(1)
(MPc)n
nMPc
← 
Solvating power of the solvent has a significant effect
on association of metallophthalocyanines. There are
UV-vis spectra of CoTSPc1 in various solvents on Fig. 1.
Figure 1 shows presence of predominantly monomeric
form of CoTSPc1 in solvents (DMF, DMSO and
Py) capable to axial coordination interaction. Molar
extinction coefficient (e) calculated with Beer–Lambert–
Bouguer law for such systems are presented in Table 1.
Molar absorption of CoTSPc1 correlates with solvent’s
parameters (DN, AN, e) and has functional dependence
of second order. This data indicates that there is influence
of not only universal solvation but of specific interaction
too on self-association process of CoTSPc1. CoTSPc1
is strongly associated in solvents capable to universal
solvation only, herewith as shown on Fig. 1 there is
significant bathochromic shift of absorption Q-band in
water and water-alkali mediums. Analysis of the work’s
results and literature data [15, 18–20] let us to suppose
that CoTSPc1 in water and water-alkali mediums
forms associates due to p-electronic interaction of two
macrocycles (H-aggregates). H-aggregates are formed
1
effect is registered when comparing H NMR spectra of
initial compound and its sulfonic acid. There is weak shift
of signals of second benzene ring’s protons of 4-sulfo-1-
1
naphtoxy substituent in H NMR. There is no such effect in
case of 2-naphtoxy substituent, so the sulfonic groups are
on two positions.Additionally, triazole group blocks access
of sulfonating agent. It causes significant steric constraints
during sulfonation of 1-naphtoxy substituted fragment of
metallophthalocyanine’s peripheral substituent.
Results of elemental analysis also show the presence of
hydrate shell on periphery of macrocycle. For CoTSPc2 ×
3
2H O calcd. (%): C, 42.01; N, 9.91; H, 4.14; S, 9.08;
2
found C, 42.29; N, 9.73; H, 4.42; S, 9.36. That is why
the sample was dried to a constant mass. IR (KBr): n,
-
1
cm 741 (C–N), 1049 (N=N), 1262 (Ar–O–Ar), 1091
(
2
C–S), 1158 (S=O in SO H). MS (MALDI-TOF): m/z
3
+
1
248.82 [M] . H NMR (500 MHz, DMSO-d ): d, ppm
6
-
5
-5
-5
Fig. 1. UV-vis spectra of CoTSPc1 in (1) DMSO (c 5.4 × 10 M), (2) DMF (c 5.3 × 10 M), (3) water-alkaline solution (c 4.9 × 10 M)
-5
-5
pH 13, (4) water (c 5.3 × 10 M), (5) Py (c 5.2 × 10 M) at 298.15 K
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 3–14

4
A. VASHURIN ET AL.
Table 1. Molar extinction monomers of MPc in organic solvents at 298.15 K
-
1
-1
Solvent
l, nm
e , M .cm
DN [23]
AN [24] Dielectric constant [23]
M
CoTSPc1
CoTSPc2
DMSO
DMF
Py
675
675
668
24420 ± 40
22350 ± 40
7340 ± 20
11900 ± 20
13320 ± 30
10510 ± 20
29.8
26.6
33.1
19.3
16
45
36.1
12.3
14.2
-5
-5
-5
Fig. 2. UV-vis spectra of CoTSPc2 in (1) DMF (c 5.2 × 10 M), (2) DMSO (c 5.3 × 10 M), (3) Py (c 5.3 × 10 M), (4) water-
-
5
alkaline solution (c 5.3 × 10 M) pH 13, at 298.15 K
due to p–s-contraction and p–p-repulsion of electronic
systems of two macromolecules. Coordination of solvent
promotes increasing of polarization of macrocycle’s
p–p-system which in turn leads to domination of p–p-
repulsion processes above the p–s-contraction processes
and to shifting of balance (1) toward monomeric form.
DMF, DMSO and Py form axial complex with CoTSPc1
due to specific solvation. It geometrically prevents
p-electronic interactions of two macrosystems.
Increasingofnumber of functionalgroupsonperiphery
of the macromolecule should promote increasing of
polarization effect of substituent on macrocycle and
electrostatic repulsion between similar charged particles.
It should cause dissociation of H-aggregates which is
typical for tetrasulfonic acid of cobalt phthalocyanine
by the solvent is changed. Increase of extinction
coefficient in the case of CoTSPc2 in Py is caused by
enhancement of the macrocycle’s p-system polarization
due to coordination interaction between CoTSPc2 and
Py. Decreasing of electronic effects of substituent on
conjugate system of metallophthalocyanine has probably
the strongest influence because of almost complete
absence of pyridine’s universal solvation interactions.
There is band of charge transition in the range of
445 nm on UV-vis spectra of CoTSPc2 solution in
DMSO. Position of charge transition band indicates
(II)
decrease of oxidation degree of Co central cation to
(I)
Co contained in metallophthalocyanine [21]. Observed
spectral changes could occur in case of self-association
processes only. In this case coordination interaction
between sulfonic group of one molecule and central metal
cation of another one is the most likely. The result of such
interaction is compensation of partially positive charge of
central metal cation. Herewith J-aggregates are formed in
solution (Fig. 3). There is hypsochromic shift on UV-vis
spectra. Formation of J-aggregates is possible because
of significant length of peripheral substituent compared
with tetrasulfonic acid of cobalt phthalocyanine [15].
Tetrasulfonicacidofcobaltphthalocyaninecoordinates
12 molecules of water and forms sandwich associate
[
19, 20]. Increasing of sulfonic group’s number from 4
to 8 leads to decreasing of CoTSPc2 solubility. This fact
is obviously caused by the increase of ionization degree
of peripheral substituents. It together with universal
solvating power of water leads to strong aggregation
of CoTSPc2. There is no dimerization of CoTSPc2 in
solutions of DMF, DMSO and Py (Fig. 2).
There is a decrease of extinction coefficient of
CoTSPc2 solutions in DMF and DMSO which allows
use to conclude that the degree of macrocycle solvation
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 4–14

A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
5
Fig. 3. H- and J-aggregates of CoTSPc
Fig. 4. The change in absorbance at a dilution of the CoTSPc1 solution in water (1) lmax 642 nm, (2) lmax 678 nm, (3) A (l642/l678
)
at 298.15 K
[
19, 20] in water medium. It is possibly due to insignifi-
solution. The ratioA /A is decreased with the increase
642 678
cant influence of electronic effects of peripheral sub-
stituent on conjugate p-system of macrocycle. In the case
of distancing the sulfonic group from the macrocycle,
this effect is not so clear. We performed investigation of
concentration dependence of optical density of CoTSPc1
solution in water (Fig. 4).
Data of Fig. 4 (curve 3) shows that relation of optical
density of dimeric macrocycle form (642 nm) and
Q-band is not linear during dilution of CoTSPc1 in water
of macrocycle concentration reaching the maximum in
-5
concentration range of about 2 × 10 M. It indicates that
association is intensified when concentration is over 2 ×
-5
10 M. Linear character of changing of optical density
means that there is absorption of only one chromophore
structure. Obviously H-aggregates absorb at 642 nm and
monomers of CoTSPc1 at 678 nm.
The contribution of monomeric and dimeric
components to the UV-vis spectrum of CoTSPc1 was
Copyright © 2015 World Scientific Publishing Company
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6
A. VASHURIN ET AL.
-5
Fig. 5. UV-vis spectra of CoTSPc1. (1) Experimental in water solution (c 7.97 × 10 M), (2) simulation spectra, (3) contribution of
dimeric forms in simulation spectra of CoTSPc1, (4) contribution of monomeric forms in simulation spectra of CoTSPc1, (5) base line
found and molar extinction coefficients were evaluated
based on that assumption by using the method of
statistical expansions on the Gaussian function [22].
Figure 5 demonstrates an example of analysis of
UV-vis spectra of CoTSPc1 solution in water.
Extinction coefficients (e ) for dimeric form of
D
CoTSPc1 in water were calculated based on extinction
coefficient (e ) for monomeric form and its equilibrium
M
concentration (Table 2).
The following equation [25] was used to calculate
Model spectra are in good agreement with experiment.
Absorption band of dimeric form is not shifted relatively
to experimental result. Q-band of CoTSPc1 dimeric form
has bathochromic shift for 20 nm relative to experimental
result. The value of 678 nm corresponds to the beginning
of balance (1) shifting toward monomeric form. This fact
is connected with our assumption that the macrocycle
could be in solutions in monomeric and dimeric forms
only, while there are associates of higher order in solution.
It is known that DN of water serving as ligand is
stability constant of H-aggregates (K ):
dim
(
2⋅e − e )⋅(1+ 4⋅K ⋅[CoTSPc1])
1
M
D
dim
2
(2)
−
(1+ 8⋅Kdim ⋅[CoTSPc1] )
(
A − A ) =
0
c
8
⋅Kdim
Stability (Table 2) of CoTSPc1 H-aggregates in
water was lower than for similar derivative without
triazole fragment in peripheral substituent [15]. This fact
demonstrates the influence of substituent’s on conjugation
contour of metallophthalocyanine and respectively on
coordination unit.
1
8, while DN of water serving as a solvent during the
universal salvation is 33 [23]. AN and e parameters are
respectively 54 and 81 [24]. The value of extinction
coefficient is correlated with DN and AN parameters for
water (shown in Supplementary material S1). In this case
the water serves as solvent because the parameter DN
found for water with relation e = f(DNsolv) is 33. There
is no relation if DN is 18. Summation of data allows us
to conclude that only H-aggregates are formed in water.
Slightly higher values of the dielectric constant obtained
by theoretical calculation are caused by the contribution
of nonspecific solvation of peripheral substituents.
There is a more complex situation for water-alkaline
medium where the influence of ionic power of solution
on association parameters should be taken into account.
Qualitatively based on electronic spectrum and analysis
of literature data [26, 27] it could be assumed that
CoTSPc2 in water-alkaline solution forms H- and
J-aggregates. Concentration dependence of optical
density of water-alkaline solution (pH 13) of CoTSPc2
is linear (Fig. 6) and obeys to Beer–Lambert–Bouguer
law at absorption wavelengths of 653 and 676 nm with
-1
-1
extinction coefficients 5580 ± 30 M .cm × 5630 ± 20
Table 2. Molar extinction monomer and dimmer forms of
CoTSPc1 and stability constants H-associates in water solution
at 298.15 K
-1
-1
M .cm respectively. Herewith the absorption band for
CoTSPc2 solution in visible range is wide enough and
has no splitting. Close values of e indicate the balance
of two chromophore form of phthalocyanine with similar
polarization of p-electronic system [28]. In case of H-
and J-aggregates it is not typical.
-
1
-1
-1
-1
-1
Solvent
e , M .cm
e , M .cm
Kdim, M
M
D
H O
2
32700 ± 40
8930 ± 20
5240 ± 80
Copyright © 2015 World Scientific Publishing Company
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A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
7
Fig. 6. UV-vis spectra and dependence of the optical density of CoTSPc2 concentration in an water-alkaline solution (pH 13) at a
-
5
-5
dilution of 7.97 × 10 M to 1.52 × 10 M at 298.15 K. (1) l 653 nm, (2) lmax 676 nm
max
-5
Fig. 7. UV-vis spectra of CoTSPc1 in water solution (c 7.97 × 10 M) in the titration DABCO at 298.15 K
Coordination properties of CoTSPc1 and CoTSPc2
dimer. Besides the geometrical factor has a big influence
on monomerization of metallophthalocyanine in solution.
Earlier[15,29]wefoundthatadditionofmonodentateligand
It is possible to control the associative monomer-
dimer balance due to axial coordination of small organic
ligands having electron donor atom. Herewith balances
may be observed in system;
(pyridine, piperidine) to solutions of cobalt phthalocyanine
sulfonic derivatives that have sulfonic groups connected by
naphthalene fragments (analogs of CoTSPc1 and CoTSPc2
without benzotriazole fragments) leads to dissociation of
H-aggregates and formation of monoligand axial complexes
in solution. Pyridine and piperidine have no second donor
atom. It does not let to vary the associates type of CoTSPc1
and CoTSPc2 in solution.

→
(3)
(4)
(
CoPc) +L
CoPc⋅L+CoPc
2
← 

→
(
CoPc) +2L
L⋅CoPc⋅L+CoPc
2
← 
From that point of view ambidentate molecule of
DABCO is very interesting. Due to the second electron
donor atom, DABCO engages in coordination interaction
with two macrocycle molecules at the same time.
Herewith dissociation of H-aggregates is not observed.
Figure 7 shows changes of UV-vis spectra of water
solution of CoTSPc1 during titration by DABCO.
.
where L — organic ligand, CoPc L — monoligand axial
.
.
complex, L CoPc L — biligand axial complex.
Phthalocyanine macrocycle compensates partially
positive charge taking additional ligand in fifth or sixth
coordination position of metal. So there are redistribution
of p-electron density in macrocycle and dissociation of
Copyright © 2015 World Scientific Publishing Company
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8
A. VASHURIN ET AL.
where c — equilibrium concentration of axial ligand,
L
A , A × A — initial, equilibrium and final values of
0
c
∞
solution’s optical density respectively.
The value of slope of the line built according to
Equation 6 for CoTSPc1 (Fig. 9) gives composition
of axial complex CoTSPc1:DABCO 1:0.5 that based
on the whole molecule of DABCO 2:1. It confirms the
assumption that sandwich-type dimmers are formed.
There are other spectral changes for titration of
water-alkaline solution of CoTSPc2 by DABCO.
Introduction of DABCO in system leads to decreasing of
absorption intensity of the band in range of 653 nm and
its hypsochromic shifting for 10 nm. The maximum of
absorption is wide enough. There are group of isosbestic
points in system. This data indicate that chromophore
system of CoTSPc2 in solution exists in several forms.
Obviously the addition of DABCO causes the rivalry
for central metal cation and there will be triple balance
observed in solution between axial complex, J-aggregate
and sandwich-type dimer. The presence of H-aggregates
Fig. 8. Sandwich dimer of CoTSPc
Data of Fig. 7 demonstrate that increasing of DABCO
concentration leads to the decrease of absorption intensity
of macrocycle’s dimeric form band and its bathochromis
shifting on 7 nm. Herewith Q-band of monomer is
almost degenerated. There is isosbestic point in range of
absorption of 605 nm. All this characterizes appearance
of new chromophore structure in solution. Obviously this
structure is dimerized CoTSPc1. Based on the structure of
CoTSPc1 and analysis of literature data [30, 31] it could be
assumed that sandwich-type dimmers are formed (Fig. 8).
Thus the system realizes the balance (5):
in that case is unlikely. Equilibrium constant (K ) of
s
-1
CoTSPc2 associated structures is 29300 ± 400 M .
The value of K shows that dimeric associates is stable
s
enough. Analysis of acceded ligands (Fig. 9) shows that
the structure unit of the associate is molecular complex
CoTSPc2 × DABCO of composition 1:2. The system
realizes balance (4).
Catalytic properties of CoTSPc1 and CoTSPc2

→
CoPc⋅DABCO⋅CoPc
(5)
2
CoPc+DABCO
←

It is well-known that compounds containing –SH
fragment may be easily oxidized by oxygen of air to
desire disulfides [32]. Soft conditions and selectivity
in such processes are explained by using catalysts
based on phthalocyanine complexes with metals [3].
Thiuramilsulfides (thiuram E and thiuram D) are products
of oxidation of thiocarbamic acids. Thiurams E and D
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)
(6)



A − A 
c
∞
Fig. 9. Bent-French line of (1) CoTSPc1; (2) CoTSPc2
Copyright © 2015 World Scientific Publishing Company
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A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
9
are compounds used in production of medicines against
presence of free hydroxyl groups in solution will affect
the ionization degree of peripheral substituents which in
turn will amplify dimerization and decreases catalytic
properties of metallophthalocyanines. From the other side
increasing of pH leads to shifting of balance (12) towards
the alcohol and drug addictions, as amplifiers of rubbers
vulcanization, in fine organic synthesis. Thiurams E and
D of good quality may be obtained during oxidation of
thiocarbamic acids with using phthalocyanine catalysts.
There are different mechanisms of RSH-compounds
oxidation to disulfides with complexes of phthalocyanines
known from literature [33–35]. The mechanism based on
possibilityoftriplecomplexformationwithfurthercleavage
–
RS anion that accelerates oxidation of the substrate.
-
+
RSH + NaOH  RS + Na + H O
(12)
2
where RSH — DTC.
Kinetic parameters of DTC oxidation using CoTSPc1
and CoTSPc2 as catalysts are given in Table 3.
·
of RS radical is the most appropriate in our opinion.
This mechanism could be presented by following
elementary stages:
Obtained kinetic data suggest similar DTC oxidation
mechanisms using CoTSPc1 and CoTSPc2 as catalysts.
It should be noted that difference of oxidation rates for
CoTSPc1 and CoTSPc2 is caused by different associative
state of macrocycle in solution as it was described above.
Catalytic activity of CoTSPc1 and CoTSPc2 is about
equal to traditionally used catalysts [3, 16, 29]. Based on
mechanism represented by Equations 7–11 the influence
of peripheral substituent nature on catalytic activity of
macrocycle will be definitely connected with effects of
formation of H-aggregates and J-aggregates which in
turn determines stability of triple complex (8). Obviously
k
−
II
1
·
I

→
(7)
(8)
RS + Co Pc
RS ⋅Co Pc

←
k
·
I
2
·
II
−
2

→
RS ⋅Co Pc⋅O
RS ⋅Co Pc + O
2
← 
k
, slowly
·
II
−
2
3
·
III
−
2

→
(9)
RS ⋅Co Pc⋅O
RS + Co Pc⋅O
←
·
quickly
2
RS   → RSSR
(10)
(11)
k
III
−
4
II

→
Co Pc + O2
Co Pc⋅O
2
← 
Previously the kinetics and mechanism of that process
in the presence of homogeneous and heterogeneous
phthalocyanine catalysts were investigated in our works
·
the stage of RS radical avulsion from triple complex is
limiting. Steric conditions of triple complex blocking in
net of CoTSPc2 associates create additional energy costs
for its destruction.
[
8, 29, 34, 36]. We showed that structure of macrocycle
and its coordination ability play the main role in catalysis.
The kinetic model may be analyzed by adopting in
The pH dependence of observed constant (k ) of
-
II
•
I
obs
Equations 7–11: A for RS , M for Co Pc, X for RS ∙Co Pc,
1
sodium N,N-diethylcarbamodithioate (DTC) oxidation
rate using CoTSPc1 and CoTSPc2 as catalysts is shown
on Fig. 10. This dependence has complex character and
reaches the maximum.
This fact is caused by cooperative influence of pH
of solution on catalyst and substrate. From one side the
•
II
-
III
-
•
B for O , X for RS ∙Co Pc∙O , X for Co Pc∙O , D for RS
2
2
2
3
2
and their concentrations for C with corresponding index.
The sum of concentrations of all complexes (C º) con-
M
taining catalysts is calculated according to the following:
C ° = C + C + CX2
M
M
X
(13)
1
Fig. 10. Dependence of kobs of DTC oxidation in the presence of phthalocyanines catalysts from the solution pH at 298.15 K.
1) CoTSPc1; (2) CoTSPc2
(
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 9–14

10
A. VASHURIN ET AL.
-5
Table 3. Kinetic parameters of the DTC oxidation in the presence of CoTSPc1 (8.07 × 10 M) and CoTSPc2
-
5
-2
(
10.08 × 10 M) in water-alkaline solution pH 9. Initial concentration of DTC 1.4 × 10 M
5
-1
≠
Macrocycle
kobs × 10 , s
E , kJ/mol
lnA
c
2
93.15
298.15
303.15
308.15
313.15
CoTSPc1
CoTSPc2
5.9 ± 0.3
3.5 ± 0.2
9.8 ± 0.2
7.5 ± 0.3
17 ± 0.4
14 ± 0.3
27 ± 0.1
35 ± 0.3
42 ± 0.5
73 ± 0.5
75 ± 4
21.02
37.29
0.73
0.84
116 ± 8
where CM — concentration of proper catalysts,
This function has linear character. Presented kinetic
model describes experimental results of aerobic DTC
oxidation in presence of catalysts CoTSPc1 and
CoTSPc2 well. In accordance to that accessibility of MPc
coordination unit is the most important factor for catalysis.
In view of high coordination activity of CoTSPc1 and
CoTSPc2 both with respect to solvents and electron
donor ligands they have all necessary properties to form
dynamic triple complexes with substrates. Such complexes
may be registered in dimeric structure that discovers
new properties of phthalocyanine compounds as agents
transporting coordinated into triple complex with organic
ligand oxygen. Avulsion of radical from triple complex
may be done in necessary delivery area, but this topic
needs further researches beyond the scope of this work.
•
I
CX1 — concentration of RS ∙Co Pc, C — concentration
X
2
•
II
-
of RS ∙Co Pc∙O .
2
Hence, the function of catalyst complexation takes the
form;
f(M) = C /C °
(14)
M
M
CX1 = k C C , C = k C C °, under condition of
1
M
A
X
2
X
B
2
1
C °@C ° and suggestion that stage 9 is limiting we have;
B
A
CX
=
k k C C C °
1
2
M
A
B
(15)
2
-
where CA — concentration of RS , C ° — initial
B
concentration of oxygen.
The rate (r) of stage (Equation 9) is calculated by the
following;
r = k C
3
X
(16)
2
Application of CoTSPc1 and CoTSPc2 as dyes
taking into account Equation 15;
r = k k k C C C °
Besides catalytic activity metallophthalocyanines
have practicable properties as dyes of natural and
synthetic fibers. There were experiments of dyeing of
wool and rayon by CoTSPc1 and CoTSPc2. It gives
pretty unexpected results. Tetrasulfophthalocyanine of
cobalt as dye was used for comparing.
(17)
3
1
2
M
A
B
Taking into account the complexation of catalyst C is
M
substituted by C °. The final equation for calculation of
M
DTC oxidation rate is the following;
Tetrasulfonic acid of cobalt phthalocyanine stains
samples into blue. Blue color expected by us for dyes
CoTSPc1 and CoTSPc2 was not obtained. However
uncommon green colors were obtained. Under similar
conditions of dyeing CoTSPc1 gives bright green fiber.
Simultaneously CoTSPc2 gives rich dark green color
(shown in Supplementary material S2 and S3).
Blue colors of rayon were obtained by staining.
Tetrasulfonic acid of cobalt phthalocyanine has almost
no dyeing effect in relation to rayon. The most saturated
color was observed in samples dyed by CoTSPc2.
ꢀ
M
ꢀ
B
k k k C C
3
1
2
.
r =
CA
(18)
ꢀ
B
1
+ k C + k k C C
1
A
1
2
A
Functionf(M)islinearwithincreasingofconcentration
C . Possible deviation from the straightness is caused by
decreasing of concentration C °.
Equation 18 is linear in coordinates Lineweaver–
Burk [37];
A
B
1
1
1
1
=
+
+
(19)
ꢀ
M
ꢀ
B
ꢀ
ꢀ
M
ꢀ
M
r
C k k k C C
k k C C
k3C
A
3
1
2
3
2
B
EXPERIMENTAL
Under condition of k k C C ° ! (1 + k C ) we have;
1
2
A
B
1
A
ꢀ
M
ꢀ
B
k k k C C
3
1
2
Reagents and methods for their preparation
.
r =
CA
(20)
1
+ k C
1
A
Solvents used in the work dimethylsulfoxide
(
DMSO), N,N-dimethylformamide (DMF), pyridine (Py)
Dependence C = f(t) in this case takes form:
A
and chloroform were purified and kept in accordance to
recommendations [38].
Inorganic salts applied for synthesis were previously
recrystallized by methods recommended in [39].
ꢀ
A
k
C
X
1
ln
+
= t
(21)
ꢀ
M
ꢀ
ꢀ
M
ꢀ
C C k k
CA C C k k
B
1
2
B
1
2
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 10–14

A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
11
1
,4-Diazabicyclo[2.2.2]octane (DABCO) and deute-
the following method: mixture of 387 mg (0.1 mmol) of
4-(1-benzotriazolyl)-5-(1-naphthoxy)phthalonitrile [40]
and 136 mg (0.05 mmol) of anhydrous cobalt chloride was
thoroughly stirred. Next, there was alloying of mixture for
one hour under the temperature of 503–510 K with further
extracting of target phthalocyanine with chloroform from
reaction mixture and columnar chromatography (sorbent-
Al O , eluent-chloroform). The yield was 360 mg (85%).
rated solvents were purchased from Aldrich. Sodium
N,N-diethylcarbamodithioate (DTC) (99%, ChemMed
Synthesis, Russia) was used without additional purification.
Equipment
Elemental analysis has been carried out by means
of chromatographic analyzer Flash HCNS-OEA 1112
Germany). The flowrates of helium and oxygen were
40mL/minand250mL/min,respectively;thetemperature
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 (USA) in 400–4000 cm
frequency range.
NMR spectra of the solutions were recorded by means
of NMR spectrometer Bruker AVANCE-500 (Germany)
at operating frequency 500 MHz ( H) and 100 MHz
2
3
Elemental analysis found: C 71.38, H 3.20, N 17.44%;
anal. calcd. for C H N O Co: C, 71.68; H, 3.26; N,
(
1
96
52 20
4
-1
1
7.42%. IR (KBr): n, cm 746 (C–N), 1041 (N=N), 1210
(Ar–O–Ar). MS (MALDI-TOF) shown in Supplementary
material S4. Synthesis of initial phthalonitriles shown in
Supplementary material S5.
-1
2
,9,16,23-Tetrakis(1-benzotriazolyl)-3,10,17,24-
tetrakis(2-naphthoxy)phthalocyaninate cobalt(II)
CoPc2). The synthesis was performed in accordance
(
to Scheme 2. 4-(1-Benzotriazolyl)-5-(2-naphthoxy)
phthalonitrile [40] was taken as starting material. Yield
was 367 mg (86%). Elemental analysis found: C, 71.60;
H, 3.04; N, 17.11%; Anal. calcd. for (C H N O Co):
1
1
3
(
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 2800 (USA) spectrophotometer in a
spectral range of 200–1000 nm. Quarts optical cell were
used for the measurements. UV-vis spectra were recorded
at 298.15 ± 0.03 K.
96
52 20
4
C, 71.68; H, 3.26; N, 17.42%. Sulfonated derivatives
were obtained according to the general method: 160 mg,
0
.1mmolofphthalocyanineCoPc1orCoPc2weredissolved
in mixture of 2 mL (18 mmol) of chlorosulfonic acid and
mL (18 mmol) of thionyl chloride. Next, it was stirred
2
at the temperature of 293 K for 2 h. Further, the reaction
mixture was poured onto ice mixed with NaCl. Obtained
precipitate was collected with Schott filter and dried in
desiccators over concentrated H SO for 72 h. Extraction of
Mass spectra were measured on an Axima MALDI-
TOF mass-spectrometer (Shimadzu, Japan).
2
4
sulphochlorides was carried out with acetone with further
drying. Sulfo-derivatives were obtained by hydrolysis of
sulfochlorides with 82–85%. Sulfochlorides was boiled
in water for complete dissolution and water was proved.
Additional purifying is carried out with chromatography
(sorbent-silica gel M 60, eluent-DMF).
Synthesis of metallophthalocyanines
2
,9,16,23-Tetrakis(1-benzotriazolyl)-3,10,17,24-
tetrakis(1-naphthoxy)phthalocyaninate cobalt(II)
CoPc1). The synthesis was performed in accordance to
(
N
N
R
N
N
N
N
R
N
Co
N
N
N
N
N
NC
NC
R
N
CoCl2 503-510 K
N
N
N
N
N
R
N
N
N
R
N
N
R =
R = 1, CoPc1
R = 2, CoPc2
or
1
O
2
O
Scheme 2. Synthesis of CoPc1 and CoPc2
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 11–14

12
A. VASHURIN ET AL.
Spectral studies
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
Spectral researches were carried out for isomolar
series of solutions. Calculation of stability constant for
molecular complex of CoPc with DABCO formation was
carried out based on changes of absorption density of
solution in range of Q-band.
6
50 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 [36].
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.
.
.
[
DABCO CoPc DABCO]
K =
(22)
s
2
.
CoPc] [DABCO]
[
Equilibrium concentration of molecular complex was
calculated as:
(
(
A - A )
0 c
0
.
cCoPc.DABCO = c
(23)
CoPc
A - A )
0
∞
Under conditions of constant concentrations of oxygen
and catalyst, constant pH of solution and the rate of DTC
oxidation is described by first order kinetic equation:
where cCoPc∙DABCO — equilibrium concentration of
0
molecular complex, c
— initial concentration of
CoPc
macrocycle. A , A and A — initial, equilibrium and final
0
c
∞
dc/dt = –kobs ∙c
(27)
values of solution’s optical density of Q-band respectively.
Concentration of free ligand was determined according
to equation:
where c — DTC concentration, t — time, k — observed
obs
-1
constant of the rate, s .
(
(
A - A )
0 c
0
0
It is confirmed by straightness of graphics in
coordinates ln c–t and constancy of rate constants
calculated according to the equation:
.
cDABCO = c
-c
(24)
DABCO
CoPc
A - A )
0
∞
Taking into account Equations 23 and 24 the formula
for calculating of stability constant will be:
kobs = (1/t)∙ln(c /c)
(28)
0
where c — initial concentration of DTC, c — current (t)
concentration of DTC.
Degree of transformation was calculated according to
Equation (29);
[
(A - A ) / (A - A )]
0
0
0
c
c
∞
K =
(25)
s
0
.
(A - A ) / (A - A )]
0 c 0 ∞
[
c
-c
DABCO
CoPc
The investigation was carried out with excess of
ligand relative to the metallophthalocyanine. That is why
equilibrium concentration of DABCO is considered to be
equal to its initial concentration. It simplified the process
of calculating of Ks:
c = (c -c )/c
(29)
0
t
0
where c — initial concentration of DTC, c — current
0
t
concentration of DTC.
Disulfide formation was monitored with FT-IR
1
13
1
A0 - A
c
spectra, and H NMR, and C NMR. H NMR of DTC to
oxidation (500 MHz, D O): d, ppm 4.34 (m, J = 15 Hz,
H, CH ); 1.39 (t, J = 5 Hz, 6H, CH ). C NMR of DTC
K =
(26)
s
0
(
A - A )c
2
0
∞
DABCO
1
3
4
2
3
to oxidation (100 MHz): d, ppm 11.65, 27.50, 49.08,
Studies of catalytic activity
-
1
2
05.02. IR of DTC to oxidation IR (KBr): n, cm 2979
The catalytic activity of metallophthalocyanines was
tested with a known [32, 36] reaction of sodium N,N-
diethylcarbamodithioate (DTC) oxidation. It process
according to general scheme 3.
Advantages of this reaction are low toxicity of initial
materials and possibility of monitoring the concentration
of initial and desired materials and identification of
reaction products using electron absorption (UV-vis
(–CH υ ), 2847 (–CH –υ ), 1476 (–CH –d), 1378
3
as
2
as
2
(–C–N st), 1269 (–C=S st), 1075, (d, –C–S).
During oxidation of DTC the formation of
diethylcarbamothioylsulfanyl-N,N-diethylcarbamodi-
1
thioate (Thiuram E) [32, 36] is observed. H NMR
of Thiuram E obtained by DTC oxidation (500 MHz,
CDCl ): d, ppm 3.71–3.77 (m, 8H, CH ); 1.29–1.23
3
2
1
3
(m, 12H, CH ). C NMR of Thiuram E obtained by
3
C H
S
C2H5
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
C2H5
SNa
Scheme 3. Oxidation of DTC
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 12–14

A NEW WATER-SOLUBLE SULFONATED COBALT(II) PHTHALOCYANINES
13
DTC oxidation (100 MHz): d, ppm 10.49, 25.72,
2.04, 51.26, 190.05. IR of Thiuram E obtained by
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