Synthesis, catalytic, spectroscopic, fluorescent and coordination properties of dicyanophenoxy-substituted phthalocyaninates of d-metals

Article abstract of DOI:10.1016/j.dyepig.2019.108018

Isomeric phthalonitriles having four terminal cyano-groups are synthesized by means of nucleophilic replacement of 4-nitrophthalonitrile's nitro-group with resorcinol and hydroquinone fragments. Corresponding phthalocyaninates of cobalt, zinc, nickel and

Full text of DOI:10.1016/j.dyepig.2019.108018

Journal Pre-proof
Synthesis, catalytic, spectroscopic, fluorescent and coordination properties of
dicyanophenoxy-substituted phthalocyaninates of d-metals
Artur Vashurin, Dmitry Erzunov, Kristina Kazaryan, Svetlana Tonkova, Tatyana
Tikhomirova, Anna Filippova, Oscar Koifman
PII:
S0143-7208(19)31556-6
DOI:
https://doi.org/10.1016/j.dyepig.2019.108018
DYPI 108018
Reference:
To appear in: Dyes and Pigments
Received Date: 5 July 2019
Revised Date: 5 September 2019
Accepted Date: 2 November 2019
Please cite this article as: Vashurin A, Erzunov D, Kazaryan K, Tonkova S, Tikhomirova T, Filippova
A, Koifman O, Synthesis, catalytic, spectroscopic, fluorescent and coordination properties of
dicyanophenoxy-substituted phthalocyaninates of d-metals, Dyes and Pigments (2019), doi: https://
doi.org/10.1016/j.dyepig.2019.108018.
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2019 Published by Elsevier Ltd.

Synthesis, catalytic, spectroscopic, fluorescent and coordination
properties of dicyanophenoxy-substituted phthalocyaninates of d-metals
a, b
a,*
b
b
Artur Vashurin , Dmitry Erzunov , Kristina Kazaryan , Svetlana Tonkova , Tatyana
b
b
a
Tikhomirova , Anna Filippova , Oscar Koifman
a
Research Insitute of macroheterocycles, Ivanovo State University of Chemistry and Technology, Ivanovo, Russia, 153000
Department of Inorganic Chemistry, Ivanovo State University of Chemistry and Technology, Ivanovo, Russia, 153000
b
@
Corresponding author E-mail: demon_erz@mail.ru
Isomeric phthalonitriles having four terminal cyano-groups are synthesized by means of nucleophilic
replacement of 4-nitrophthalonitrile’s nitro-group with resorcinol and hydroquinone fragments.
Corresponding phthalocyaninates of cobalt, zinc, nickel and copper are obtained based on the compounds.
The synthesized metal phthalocyaninates are studied in terms of spectroscopic properties using various
organic solvents and additionally organic bases. Synthesized cobalt and zinc phthalocyaninates are found to
form stable sandwich-type dimers while reacting with 1,4-diazabicyclo[2.2.2]octane (DABCO).
Phthalocyaninates having substituted para-positions form more stable sandwich-type agregates than meta-
substituted ones. A stability of molecular complexes of 1:1 composition obeys the following order: Py < Pz <
DABCO for all synthesized phthalocyaninates.
Keywords: Pthalocyanines, d- metals complexes, synthesis, spectroscopic-luminiscent properties, catalysis,
aggregation
1
. Introduction
1
,2
3
Metal phthalocyanines have become widespread as effective elements of optics devices and electronic systems , stable
4
5,6
dyes and pigments, sensitizers as well as highly selective catalysts . Such a wide application range originates from the
compounds being specific and unique in properties that is reflected by features of the structure, existence of π-conjugated
macrocycle core and easyness of modifying preipheral and non-peripheral substituents. One can fine tune properties of
1

7
resulting compounds by varying central metal and peripheral substituents. The most prevalent role of phthalocyanine metal
complexes in industry is catalysis where the compounds can effectively and selectively catalyze demercaptanization of oil
8
,9
fractions. To date for purposes mentioned above catalysts based on metal phthalocyaninates having aromatic fragments
bonded to each other in a harsh way are appllied. Such a bonding deprives a molecule of flexibility working its catalytic
activity because of sterical hindrance in coming closer of a substrate and an oxidizer with central metal atom. Extension of
10,11
the periphery by fragments bonded to each other flexibly is one of ways out
.
Cyano-substituted phthalocyaninates are of certain interests being precursors for polyphthalocyanine structures
1
2–18
covalently bonded through a periphery
. Such systems are applicable due to nonlinear optical properties of third order
One can synthesize both homo- and hetero-polymetal structures by utilizing various central metal atoms. It allows fine
selective tuning properties of a resulting material depending on necessity. In addition tetrapyrrolic macroheterocycles are
1
9,20
.
21
known to be prone to aggregation . Aggregation is a prominent, naturally occurring phenomenon that involves automatic
formation of dimers and higher aggregate of various and often complex structures. Aggregation of phthalocyanines
22
proceeds in different ways including with small organic ligands . These applications arise from the MPc conjugated π-
system, an ability of central cavity to coordinate various ligands and their chemical and physical stability. MPcs can be
tuned for different applications by substituting certain position of the macrocycle.
Aggregation is known to affect catalytic properties of phthalocyaninates dramatically. Extension of the periphery
with spatially-flexible substituents can provide disaggregation of the molecules due to sterical factor.
Thus, this work is devoted to the preparation of new phthalocyaninates of cobalt, zinc, copper, and nickel with
cyanophenoxyl peripheral fragments. The presence of acceptor cyano groups and oxygen atoms provides a shift in electron
density from the macrocycle to the periphery, favoring the occurrence of catalytic reactions, along with the flexible structure
of substituents due to the presence of oxygen bridges. Based on the obtained phthalocyaninates with terminal cyano groups,
it is planned to obtain oligo- and polymeric multinuclear phthalocyanine structures.
RESULTS AND DISCUSSION
Synthesis of 4,4'-[1,Х-phenylenbis(oxy)]diphthalonitriles
4
,4'-[1,4-Phenylenbis(oxy)]diphthalonitrile and 4,4'-[1,3-phenylenbis(oxy)]diphthalonitrile were synthesized by
nucleophilic replacement of 4-nitrophthalonitrile’s (1) nitro-group with corresponding isomers of dihydroxybenzene. The
reaction was carried out in anhydrous DMF accompanied with addition of potassium carbonate (Scheme 1). Reaction
mixture was being stirred for 48 h under 25°С. The reaction was controlled by means of thin-layer chromatography (SiO2)
2

utilizing ethanol as eluent. In order to extract phthalodinitriles 2 and 3 the reaction mixture was poured into 0.1 M water-
alkali solution, the precipitate was filterred off and washed with water. Then the precipitate was washed with water-alkali
solution and water until neutral pH. Excess of a solvent was removed under vacuum. Recrystallization of the compounds
was performed from ethanol. Yield of compounds 2 and 3 was 65 and 76% respectively.
Scheme 1. Meta- and para- phenylenebisoxy-substituted diphthalonitriles synthesis route
Compounds 2 and 3 were structurally characterized by means of IR, NMR spectroscopies and MALDI-TOF
-1
-1
spectrometry. The IR spectra represent the whole set of characteristic vibrations at 2232-2243 cm υ(С≡N), 1243-1256 cm
-1
-1
υ(Ar–O –Ar), 1389-1597 cm υ(С =C ), 2850-3065 cm υ(C –H). Completeness of+ nucleophilic replacement was also
ar
ar
ar
being monitored by IR-spectroscopy method. IR spectra of 2 and 3 contain no bands characterizing symmetric (1340-1350
-1
-1
cm ) and asymmetric (1560-1565 cm ) vibrations of nitro-group’s N=O bond evidencing compound 1. Additionally, the
-1
band at 1243-1256 cm appears reflecting skeleton vibrations of Ar-O-Ar group resulting from the reaction.
MADLI-TOF mass-spectra of high definition obtained for 2 and 3 represent molecular signals of m/z equal to
3
62.11 and 362.09 respectively (Supplementary).
1
Individuality of obtained compounds 2 and 3 is proved by position, quantity and shape of signals found in Н and
1
3
С spectra (Supplementary) as well as by absence of impurities signals. Para-substitution of resulting dinitrile provides
1
notable shift of all signals to weak field compared to corresponding proton signals registered for meta-one in Н NMR
13
spectrum. С spectrum in contrary contains negligible shift (about 1.5-2 ppm) to strong field.
Meta-substitution noteworthy yields higher for 11% compared to similar para-substitution most probably due to
steric factor. Corresponding phthalocyaninates of d-metal were obtained based on phthalodinitriles 2 and 3.
Synthesis of d-metal phthalocyaninates
Synthesis of the phthalocyaninates is carried out by template melting technique utilizing corresponding nitrile and
anhydrous acetate of nickel, cobalt, zink or copper under temperature of 190-195 °С for 30 minutes (till complete
3

crystallization) (Scheme 2). Obtained mixture after cooling is replaced on Shotts filter and washed with water and ethanol
in order to remove traces of a salt and a nitrile. Chloroform (for Co and Zn complexes) or acetone (for Ni and Cu
complexes) are applied in order to extract desired compound and separate it from polyphthalocyanine fractions. The solvent
is removed and the complex is purified by means of column chromatography (SiO ) utilizing chloroform (Co, Zn-
2
complexes) or chloroform-acetone mixture (10:1, Ni, Cu-complexes) as eluent.
Scheme 2. Synthesis of Co(II), Zn(II), Ni(II), Cu(II) tetrakis-(dicyanophenoxy)phthalocyanines
Compounds 4-11 were identified with help of IR and NMR spectroscopies as well as MALDI-TOF spectrometry.
All obtained metal complexes give mass-spectra representing molecular signal while signals of di- and poly-phthalocyanine
systems absent (Fig. 1).
Fig. 1. MALDI-TOF mass spectra of cobalt (а - 4, b – 5) and zinc (c - 6, d -7) complexes
4

Corresponding IR-spectra for 4-11 represent whole set of characteristic bands (Supplementary). Besides, a
phthalocyanine metal complex originated from corresponding dinitrile has more intensive band responding to vibrations of
-1
С≡N group (~ 2232 cm ) that is explained by bigger number of such a groups.
1
Н NMR spectra of the metal complexes has no extraneous signals and spectrum of each set of metal
phthalocyaninates has general view (supplementary) accompanied with a signals shift for 0.02-0.03 ppm to weak field
according to the following order Cu – Zn – Ni – Co.
Highest yields are reached in case of Co(II) used as central metal, lowest – in case of Cu(II). In general, yield is
higher in case of para-substituted molecules compared to meta-substituted ones.
Spectroscopic and coordination properties of Co(II) and Zn(II) phthalocyaninates
23
Zinc and cobalt complexes are the most prospective as materials for catalysts and photocatalysts . This is due to
their ability to coordinate additional ligands into fifth and sixth positions resulting in labile molecular complexes. For the
beginning all obtained compounds were studied spectroscopically in various solvents (Table 1). There was no deviations
from the Lambert-Bouguer-Beer law observed upon study of concentration dependence for solutions of the
phthalocyaninates in DMSO, Py, acetone and DMF. Absence of the deviations is explained by specific solvation of central
metal cation by the chosen solvents. One can conclude the macrocyclic chromophore under such conditions maintains
constant. A shape of a spectrum (Fig. 2) indicates the chromophore to be monomeric.
a
b
-6
-5
-5
Fig. 2. UV-vis spectra of complexes 4 (а) in 1) Py (2.91×10 M), 2) DMF (1.51×10 M), 3) DMSO (2.86×10 M), 4)
-6
-5
-6
-6
Acetone (1.34×10 M), 5) CHCl (4.41×10 M) and 7 (b) in 1) Py (3.32×10 M), 2) DMF (3.31×10 M), 3) DMSO
3
-6
-6
-6
(
3.33×10 M), 4) Acetone (3.67×10 M), 5) CHCl (2.91×10 M).
3
5

Meta-substituted complexes of Co(II) and Zn(II) exhibit greater values of extinction compared to para-analogues.
Moreover, exchange of Co for Zn is accompanied with increasing extinction coefficients. Varying a solvent does not affect
the shape of spectrum but shift Q-band bathochromically or hypsochromically (Fig. 2). The most significant red shift of the
band for CoPc and ZnPc is observed in DMF. The greates blue shift responds to DMSO.
Table 1. Spectroscopic characteristics of phthalocyanines 4-7 in various organic solvents
λ, нм (lgε)
Compound
Me
DMSO
62
4.03)
63
3.61)
79
Py
Acetone
664
CHCl3
669
DMF
6
662
4
5
6
7
675 (4.48)
(
(
(
(
(3.99)
664
(4.42)
665
(4.48)
673
Co
6
677 (3.63)
(3.55)
678
(3.67)
671
(4.47)
679
6
675
4.59)
680
(4.38)
680
(4.61)
673
(4.55)
681
(4.52)
Zn
678 (4.33)
4.44)
(4.28)
(4.45)
(4.59)
-5
Chloroform solutions of CoPc and ZnPc upon reaching 5.7×10 M concentration and further increase (Fig. 3)
exhibit deviation from linearity indicating appearance of new macrocyclic form within the solution. The form is supposed to
be Н-aggregate.
6

Fig. 3. UV-vis spectrum changes under dilution of Zn(II) phthalocyanie (7) solution in CHCl at concentration range from
3
-5
-6
7
.32×10 M to 3.06×10 M. Insertion – the deviations observed from the Lambert-Buger-Beer’s law for phthalocyaninates
-5
4
(a), 5 (b), 6 (c), 7 (d) at the concentrations about 5.7×10 M.
Interaction between phthalocyaninates and ligands has been studied in order to find aggregation type out. Position
of Q-band shifts during titration of CoPc and ZnPc chloroform solutions by pyridine. Spectroscopic behavior is changed
indicating axial coordination of pyridine by central metal cation. Addition of pyridine to chloroform solution of CoPc1
causes negligible (up to 5 nm) hypsochromic shift of Q-band that could be caused by appearance of association equilibrium
due to increasing solvating ability of mixed solvent (chloroform-pyridine) toward macrocycle periphery. Coordination
parameters of pyridine are presented in Table 2. All studied phthalocyaninates additionally coordinate only one pyridine
molecule into axial position of the metal. Values of thermodynamic constants obtained for pyridinate complexes of studied
phthalocyanines (Table 2) indicates their low stability.
Table 2. Thermodinamical parameters of phthalocyanines complexes 4-7 formation with pyridine and characteristics of
pyrazine and DABCO aggrerates stability
lgK
s
β
Py
Pz
DABCO
Compound
M
MPc·L
2.67
(MPc ·L )
MPc ·L3
2
2 3
2
4
5
6
7
2.51
2.73
2.48
2.87
4.75
4.71
4.74
4.67
Co
Zn
2.47
2.39
2.42
Exchange of pyridine with pyrazine used for titration causes significant decrease of Q-band intensity, its
bathochromic shift and widening (Fig. 4). Titration curve consists of two steps (supplementary). The first step corresponds
to bonding between pyrazine molecule and phthalocyanine macrocycle forming 1:1 complex. Higher concentration of
2 2 n
pyrazine contributes complexation of molecular complexes resulting in an aggregate of general composition (MPc L ) .
Bathochromic shift of Q-band is most probably explained by displacement of macrocycles’ dipole moments relative to each
7

other (aggregation type is close to J-dimers). Bant-Frech calculation results n equal to 3. A stability of such aggregates is to
be determined in first by sterical factor of peripheral substituents.
Fig. 4. Spectroscopic changes under tittration of cobalt phthalocyanine (5) solution by pyrazine solution (0.22 M) in CHCl
3
.
Insertion – Bent-French line of phthalocyanines 4 (a), 5 (b), 6 (c), 7(d).
In contrast to pyrazine titration of chloroform solutions of CoPc and ZnPc by DABCO results in hypsochromic
shift up to 10 nm. Figure 5 provides parallel disposition of macrocyclic molecules being part of an H-aggregates. The
following equilibria occurs upon titration by DABCO:

→
 →
MPc⋅DABCO+ DABCO DABCO⋅MPc⋅DABCO
MPc+DABCO
←

←
(MPc) ⋅(DABCO)3

→
MPc⋅DABCO + MPc⋅(DABCO)2
←
2
-5
Fig. 5. Spectroscopic changes under titration of cobalt phthalocyanine (5) (7.32×10 M) solution by DABCO solution (0.22
M) in CHCl . Insertion – Bent-French line of phthalocyanines 4 (a), 5 (b), 6 (c), 7(d).
3
8

Composition of complexes calculated for every step of titration proves equilibria described above. The first step is
coordination of one or two DABCO molecules. Molecular complexes are accumulating till certain concentration when
starting to interact with each other forming sandwich-type dimers. Final composition of the complex is MPc:L 2:3. In this
way, in contrast to pyrazine forming coordination oligomers consisting of macrocyclic molecules linked through ligand
bridge DABCO provides formation of dimeric structures. A stability of dimeric structures containing DABCO is mush
higher compared to aggregates with pyrazine (Table 2).
Table 3. Catalytic parameters of complexes 4-11 in DTC oxidation reaction
Co
Zn
Cu
Ni
Subst.
χ,
χ,
χ,
k
obs
k
obs
k
obs
k
obs
χ, %
%
%
%
m-
p-
19.4
16.8
34
36
6.5
6.8
14
16
6.8
7.4
9
8
3.4
4.9
7
8
The liquid-phase oxidation of DTC in the presence of phthalocyaninates synthesized proceeds more selectively
than non-catalytic oxidation. The reaction rate of DTC convertion to tetraethylthiuram disulfide increases up to 19 times in
the case of CoPc1. The kinetic curves for all the compounds studied are linear and obey the first-order kinetic equation. The
data of Table 3 show the range of catalytic activity of the compplexes synthesized is as follows: CoPc (m-) > CoPc (p-) >
CuPc (p-) ≥ CuPc (m-) ≥ ZnPc (p-) ≥ ZnPc (m-) > NiPc (p-) > NiPc (m-). As expected, cobalt phthalocyaninates are the
most active in the series due to the larger partially uncompensated charge on the central metal cation in the macroring.
Nickel phthalocyaninates turned out to be the most catalyt
ically disadvantageous due to the high coordination
saturation of the bonds between the metal and the macrocycle, which leads to a low ability to coordinate additional axial
ligands. Unexpectedly close activity was shown by complexes of copper and zinc, which in this case is obviously associated
with the steric and electronic effects of peripheral substituents, which are exerted on the macrocyclic core. A correlation is
observed between a series of catalytic activity of the phthalocyaninates obtained and the stability of their 1 : 1 molecular
complexes (Table 2), which indirectly confirms the course of the oxidation of DTC by the coordination mechanism.
In the phthalocyanine macrocomplex, metals have four bonds with a ligand, namely, two coordination and two
covalent ones. Due to the specificity of the electronic structure of the macrocyclic ligand and the presence of aligned π-
conjugation in it, all metal-ligand bonds are aligned and they begin to manifest a single nature. Thus, this leads to complete
9

2
4-25
coordination saturation of nickel in the phthalocyanine macrocomplex
. Taking into account the coordination mechanism
of the manifestation of the catalytic activity of phthalocyanines during the oxidation of sulfur-containing organic
26-29
substrates
, considered in this article, the presence of complexation, as well as the formation of a stable triple oxidizing-
phthalocyanine-substrate complex, is an integral part of the catalytic act. In this regard, the coordination saturation of nickel
leads to the possibility of the formation of only a monodentate complex of nickel phthalocyaninate either with an oxidizing
agent or with a substrate, the stability of which complicates the process of ligand elimination and electron pair exchange in
the ternary complex. In this regard, the probability of the formation of such ternary complexes in the case of nickel
phthalocyaninates is less than in the case of complexes with cobalt and copper, which is a key factor affecting the cat
activity of these complexes in the oxidation reaction of sulfur-containing compounds. Meanwhile, the close cat activity of
cobalt and zinc is quite natural for this reaction due to the fact that in addition to the electric factor, the presence of a
successful geometric arrangement of metal cations in the metal complex is essential. Due to the Jahn-Teyler effect, a change
in the geometry of the structures of cobalt and zinc complexes occurs, which favors the occurrence of the catalytic act on the
one hand, but the insufficient amount of partially uncompensated charge on the central metal ion in the case of the zinc
3
0
complex leads to a decrease in its activity due to a decrease in the likelihood of the formation of a triple complex . Thus,
the close activity between the cobalt and zinc complexes can be explained by the fact that, in the case of the zinc complex,
the geometric factor is predominant, and in the case of cobalt, the electronic structure factor of the macrocycle.
In the study of the fluorescent properties of complexes 4-7, a number of regularities were revealed (Table 4). So, in
the general case, during the transition from cobalt complexes to zinc complexes, a regular increase in the fluorescence
quantum yields is observed. Meta-substituted analogues of zinc phthalocyaninates show large values of quantum yields
compared with para-analogues, which is probably due to steric effects. The study of the fluorescence quantum yields of
aggregates of complexes with pyrazine and DABCO showed that, in general, this type of interaction leads to an increase in
the fluorescence properties.
Table 4. Quantum yields of free metalcomplexes 4-7 and their aggregates with pyrazine and DABCO in pyridine and
CHCl
3
System
Py
4
5
6
7
0.37%
0.52%
0.03%
0.00%
0.09%
0.08%
4.18%
4.23%
8.02%
5.18%
6.16%
12.27%
CHCl3
Pz
Py
1
0

CHCl3 0.06%
0.10%
0.01%
0.02%
11.56% 15.73%
DABCO Py
0.02%
5.80%
7.93%
5.40%
CHCl3 0.17%
10.49%
Thus, in the study of aggregates with pyrazine, an increase in the fluorescence quantum yields by 1.5–2 orders of magnitude
was observed, and in the case of DABCO up to 1.5 times. Finally, during the transition from pyridine to chloroform, an
increase in the fluorescence quantum yields of complexes 4–7 was determined.
CONCLUSIONS
Isomeric diphthalonitriles were synthesized during the work. Based on the diphthalonitriles corresponding
phthalocyaninates of cobalt(II), zinc(II), nickel(II) and copper(II) were obtained. The compounds were isolated, purified and
1
identified. Meta-substitution was found to yield higher compared to para-substitution. Shift of Н NMR proton signals to
weak field was revealed in Cu – Zn – Ni – Co series. Obtained compounds were spectroscopically studied in various
organic media. Meta-substituted metal complexes demonstrates greater values of extinction coefficients. Cobalt and zinc
phthalocyaninates being part of chloroform solution were found to form dimeric sandwich-type structures while interacting
with DABCO, whereas interaction with pyrazine leads to formation of oligomeric structures close to J-type aggregates.
EXPERIMENTAL SECTION
Equipment and reagents
-1
IR spectra were recorded by means of Fourier-IR spectrophotometer Avatar 360 (USA) in 400-4000 cm
frequency range. The samples were obtained by grinding corresponding crystallic compound combined with anhydrous
potassium bromide taken in 1 :100 ratio until homogeneous composition followed with tablet pressing. All data presented in
the work was gaining in transmission mode.
Electronic absorption spectra were recorded by means of spectrophotometer UNICO 2800 in 300-1100 nm range
utilizing quartz cuvettes of optical path length equal to 1 cm.
NMR spectra were recorded by means of «Bruker AVANCE 500» spectrometer (TMS is inner standard)
1
13
registering Н and С nuclei at 500 and 125 MHz frequencies respectively.
Mass-spectra were registered by means of time-of-flight mass-spectrometer «Simadzu Axima Confidence»
-3
(
MALDITOF MS). Samples of approximately 10 M concentration were stored in tetrahydrofurane and CHCA (alpha-
Cyano-4-hydroxycinnamic acid) was used as a matrix.
Purification of the compounds was performed utilizing silica gel 60 (230-400 mesh).
1
1

4
-Nitrophthalonitrile (99%, «Sigma-Aldrich»), chloroform (99%), Dimethylformamide (DMF) (99%), Dimethylsulfoxide
(
DMSO) (99%) pyridine (Py) (99%), acetone (99%), resorcinol (98%) hydroquinone (98%, «Sigma-Aldrich»), 1,4-
Diazabicyclo[2.2.2]octane (DABCO) (99.5%, «Sigma-Aldrich»), pyrazine (Pz) (99%, «Sigma-Aldrich») were applied
without additional purification. Sodium hydroxide, potassium carbonate and acetates of cobalt(II), zinc(II), nickel(II) and
copper(II) were purified and dehydrated right before the experiment according to common techniques.
The homogeneity of the products was tested in each step by TLC (SiO2).
The study of catalytic ativity
The experiment carried out using standard Sodium N,N-diethylcarbamodithioate oxidation reaction. The rection involved
was carried out in special constructed cell with volume of 650 ml. The standard temperature was maintained 298.15 K with
an accuracy of ± 0.05 K. Air was supplied via microcompressor with a constant rate of 2 l/min.
After the temperature of the reaction mixture becomes constant, solution was mixed, the sample of 2 ml was selected to
determine initial concentration and compressor was turned on. The moment of air supply was the beginning of the reaction.
Samples of 2 ml were taken at regular intervals during the experiment to determine the current concentration of the DTC.
Method of DTC determination: sample of 2 ml was moved to the flask of 25 ml and 4ml of CuSO4 solution with
concentration of 0.08 M was added. It leads to the formation of dark-brown precipitate – the complex of copper with DTC.
Then mixture was stirred. After this 5 ml of chloroform and 0.05 ml of 50% acetic acid was added to the resulting solution.
Then it was extracted for 1.5 min. The organic layer was moved into a volumetric flask of 25 ml, and the remaining water
solution of the Cu-DTC complex was extracted again to improve the accuracy of analysis. Collected solution of copper
complex with DTC was diluted to the exact volume. The optical density of the solution was determined at a wavelength of
4
36 nm. DTC concentration was calculated with help of the known molar extinction coefficient.
13
1
Disulfide formation was monitored with FT-IR, 1H NMR, and C NMR spectra. H NMR of DTC to oxidation (500
13
MHz, D O): δ 4.34 (m, J = 15 Hz, 4H, CH ); 1.39 (t, J = 5 Hz, 6H, CH ). C NMR of DTC to oxidation (100 MHz): δ
2
2
3
-1
1
1
1.65, 27.50, 49.08, 205.02. IR of DTC to oxidation IR (KBr): υ, cm 2979 (-CH υ ), 2847 (-CH - υ ), 1476 (-CH - δ),
3 as 2 as 2
378 (-C-N ), 1269 (-C =S ), 1075, (d, -C-S).
st
st
During oxidation of DTC the formation of diethylcarbamothioylsulfanyl-N,Ndiethylcarbamodithioate (Thiuram E) is
1
observed. H NMR of Thiuram E obtained by DTC oxidation (500 MHz, CDCl
3
): δ 3.71-3.77 (m, 8H, CH
2
); 1.29-1.23 (m,
1
3
1
2H, CH
3
). C NMR of Thiuram E obtained by DTC oxidation (100 MHz): δ 10.49, 25.72, 52.04, 51.26, 190.05. IR of
-1
Thiuram E obtained by DTC oxidation IR (KBr): υ, cm 2974 (-CH υ ), 2861 (-CH - υ ), 1505 (-CH - δ), 1380 (-C-N ),
3
as
2
as
2
st
1
273 (-C=S ), 1143, 995 (-S-S-).
st
Synthesis
1
2

Synthesis of 4,4'-[1,3-phenylenebis(oxy)]diphthalonitrile (2)
-Nitrophthalonitrile (1.00 g, 5.77 mmol) and resorcinol (0.32 g, 2.88 mmol) were dissolved in 100 ml of dry DMF. After
4
stirring for 1 h at room temperature, finely ground anhydrous potassium carbonate (0.99 g, 2.5 mmol) was added to the
described solution. The reaction mixture was stirred at 25 °C for 48 h and then it was poured into 300 ml of 0.1 M NaOH
aqueous solution. The resulting precipitate were filtered off and washed with deionized water (2 × 30 ml), 0.1 M aqueous
solution of NaOH (2 × 30 ml) and finally with deionized water (2 × 30 ml) until neutral pH. Obtaining coarse crude crystals
were recrystallized form ethanol to remove any residual of reagents. The pure product was obtained as light yellow powder
-1
and it was soluble in chloroform, ethanol, and acetone. Yield 0.68 g (65%) mp 190°C. FT-IR: νmax, cm 3088, 2917, 2850
1
(
C
ar – H); 2243 (C≡N); 1586, 1474, 1389 (Car = Car); 1256 (Ar–O–Ar). H NMR (500 MHz, CDCl
3
): δ, ppm 7.76 (dd, 2 H, J
4
4
3
3
=
8.6); 7.55 (t, 1 Н, J = 8.3); 7.32 (d, 2 Н, J = 2.5); 7.29 (dd, 2 Н, J = 2.5, J = 8.3); 6.99 (dd, 2 Н, J = 8.3, 4J = 2.2)); 6.82
4
13
(
m, 1 Н, J = 2.2). C NMR (100 MHz, Acetone-d ): δ, ppm 160.66, 155.52, 135.65, 132.35, 122.03, 117.91, 117.66,
6
+
1
15.10, 114.74, 112.85, 109.91. MS (MALDI-TOF): m/z 362.11 [M] , calcd. 363.08.
Synthesis of 4,4'-[1,4-phenylenebis(oxy)]diphthalonitrile (3)
-Nitrophthalonitrile (1.00 g, 5.77 mmol) and hydroquinone (0.32 g, 2.88 mmol) were dissolved in 100 ml of dry DMF.
4
After stirring for 1 h at room temperature, finely ground anhydrous potassium carbonate (0.99 g, 2.5 mmol) was added to
the described solution. The reaction mixture was stirred at 25 °C for 48 h and then it was poured into 300 ml of 0.1 M
NaOH aqueous solution. The resulting precipitate were filtered off and washed with deionized water (2 × 30 ml), 0.1 M
aqueous solution of NaOH (2 × 30 ml) and finally with deionized water (2 × 30 ml) until neutral pH. Obtaining coarse crude
crystals were recrystallized form ethanol to remove any residual of reagents. The pure product was obtained as light yellow
-1
powder and it was soluble in chloroform, ethanol, and acetone. Yield 0.79 g (76%) mp 190°C. FT-IR: νmax, cm 3065, 2924,
1
2
850 (C – H); 2232 (C≡N); 1597, 1562, 1479 (C = C ); 1243 (Ar–O–Ar). H NMR (500 MHz, CDCl ): δ, ppm 8.01 (d, 2
ar
ar
ar
3
13
Н, J = 8.7); 7.64 (d, 2 Н, J = 2.5); 7.48 (dd, 2 Н, J = 8.7, 2.6); 7.35 (s, 4 Н). C NMR (100 MHz, Acetone-d ): δ, ppm
6
+
1
58.36, 154.87, 134.99, 122.12, 120.63, 120.09, 116.70, 116.13, 115.67, 107.79. MS (MALDI-TOF): m/z 362.09 [M] ,
calcd. 363.08.
General way to synthesis tetrakis-(dicyanophenoxy)phthlocyaninetes of Co (4, 5), Zn (6, 7), Ni (8, 9) and Cu (10, 11).
A mixture of compound 2 or 3 (0.20 g, 0.55 mmol) and anhydrous salt of corresponding metal (0.13 mmol) were heated in
ceramic crucible for 30 min at 195-200°C. Rough purification was performed by filtration of fusion products on the Schott
filter with chloroform to remove residual of polymeric phthalocyanines forms. Further, the solvent was evaporated and the
filtrate was subjected to purification using column chromatography (SiO ; CHCl ).
2
3
Co(II) tetrakis-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (4)
1
3

-1
Yield 0.137 g (66 %). FT-IR: νmax, cm 3037, 2958, 2921, 2847 (C – H); 2236 (C≡N); 1591, 1473, 1405 (C = C ); 1245
ar
ar
ar
1
(
Ar–O–Ar). H NMR (500 MHz, THF-d ): δ, ppm 7.92 (s, 4 H), 7.91 (s, 4 H), 7.59 (dd, 8 H, J = 8.7, 2.5 Hz), 7.53 (t, 4 H, J
8
=
2.2 Hz), 7.42 (dd, J = 8.3, 2.2 Hz, 4 H), 7.40 (dd, J = 8.4, 2.3, 4 H), 7.05 (dd, J = 8.3, 2.2 Hz, 4 H), 7.03 (dd, J = 8.2, 2.2
+
Hz, 4 H), 7.00 (s, 4 H). MS (MALDI-TOF): m/z 1508.43 [M] , calcd. 1508.33. Anal. calcd for C H N O Co: C 70.08, H
88
40 16
8
2
.67, N 14.86, O 8.49, Co 3.91; found: C 70.07, H 2.65, N 14.86, O 8.52, Co 3.90.
Co(II) tetrakis-[4-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (5)
-1
Yield 0.143 g (69 %). FT-IR: νmax, cm 3020, 2924, 2853 (Car – H); 2233 (C≡N); 1561, 1489 (Car = Car); 1246 (Ar–O–Ar).
1
H NMR (500 MHz, THF-d
8
): δ, ppm 7.74 (s, 4 H), 7.73 (s, 4 H), 7.29 (d, 8 H), 7.25 (d, J = 2.5 Hz, 4 H), 7.24 (d, J = 2.5
+
Hz, 4 H), 7.12 (s, 16 H). MS (MALDI-TOF): m/z 1508.16 [M] , calcd. 1508.33. Anal. calcd for C88
H
40
N
16
O
8
Co: C 70.08, H
2
.67, N 14.86, O 8.49, Co 3.91; found: C 70.06, H 2.64, N 14.87, O 8.51, Co 3.93.
Zn tetrakis-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (6)
-1
Yield 0.127 g (61 %). FT-IR: νmax, cm 3081, 2923, 2850 (C – H); 2232 (C≡N); 1591, 1482, 1422 (C = C ); 1245 (Ar–
ar
ar
ar
1
O–Ar). ). H NMR (500 MHz, THF-d ): δ, ppm 7.90 (s, 4 H), 7.88 (s, 4 H), 7.56 (dd, J = 8.2, 2.1 Hz, 8 H), 7.50 (t, J =2.2
8
Hz, 4 H), 7.39 (dd, J = 8.2, 2.1 Hz, 4 H), 7.38 (dd, J = 7.9, 2.2 Hz, 4 H), 7.03 (dd, J = 8.3, 2.3 Hz, 4 H), 7.02 (dd, J = 7.9, 2.1
+
Hz, 4 H), 6.97 (s, 4 H). MS (MALDI-TOF): m/z 1515.13 [M] , calcd. 1514.77. Anal. calcd for C H N O Zn: C 69.78, H
88
40 16
8
2
.66, N 14.80, O 8.45, Zn 4.32; found: C 69.80, H 2.65, N 14.79, O 8.46, Zn 4.33.
Zn tetrakis-[4-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (7)
-1
Yield 0.123 g (59 %). FT-IR: νmax, cm 3078, 2921, 2853 (Car – H); 2233 (C≡N); 1561, 1498, 1482 (Car = Car); 1244 (Ar–
O–Ar). 1H NMR (500 MHz, THF-d ): δ, ppm 7.72 (s, 4 H), 7.70 (s, 4 H), 7.26 (d, J = 2.5 Hz, 8 H), 7.22 (d, J = 2.5 Hz, 4
8
+
H), 7.20 (d, J = 2.6 Hz, 4 H), 7.09 (s, 16 H). MS (MALDI-TOF): m/z 1515.09 [M] , calcd. 1514.77. Anal. calcd for
C H N O Zn: C 69.78, H 2.66, N 14.80, O 8.45, Zn 4.32; found: C 69.80, H 2.64, N 14.80, O 8.47, Zn 4.34.
8
8
40 16
8
Ni(II) tetrakis-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (8)
-1
Yield 0.089 g (43 %). FT-IR: νmax, cm 3069, 2961, 2924, 2853 (C – H); 2233 (C≡N); 1591, 1473, 1412 (C = C ); 1247
ar
ar
ar
1
(
Ar–O–Ar). H NMR (500 MHz, THF-d ): δ, ppm 7.92 (s, 4 H), 7.90 (s, 4 H), 7.59 (dd, J = 8.1, 2.1 Hz, 8 H), 7.52 (t, J = 2.2
8
Hz, 4 H), 7.41 (dd, J = 7.9, 2.2 Hz, 4 H), 7.40 (dd, J = 8.0, 2.1 Hz, 4 H), 7.04 (dd, J = 8.2, 2.2 Hz, 4 H), 7.03 (dd, J =8.1, 2.2
+
Hz, 4 H), 7.00 (s, 4 H). MS (MALDI-TOF): m/z 1508.06 [M] , calcd. 1508.09. Anal. calcd for C88
H
40
N
16
O
8
Ni: C 70.09, H
2
.67, N 14.86, O 8.49, Ni 3.89; found: C 70.10, H 2.66, N 14.85, O 8.51, Ni 3.90.
Ni(II) tetrakis-[4-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (9)
-1
Yield 0.079 g (38 %). FT-IR: νmax, cm 3072, 2923, 2854 (C – H); 2231 (C≡N); 1490, 1412 (C = C ); 1236 (Ar–O–Ar).
ar
ar
ar
1
H NMR (500 MHz, THF-d ): δ, ppm 7.73 (s, 4 H), 7.71 (s, 4 H), 7.27 (d, J = 2.5 Hz, 8 H), 7.23 (d, J = 2.5 Hz, 4 H), 7.21
8
1
4

+
(
d, J = 2.6 Hz, 4 H), 7.10 (s, 16 H). MS (MALDI-TOF): m/z 1508.19 [M] , calcd. 1508.09. Anal. calcd for C H N O Ni:
88 40 16 8
C 70.09, H 2.67, N 14.86, O 8.49, Ni 3.89; found: C 70.11, H 2.66, N 14.86, O 8.50, Ni 3.91.
Cu(II) tetrakis-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (10)
-1
Yield 0.135 g (65 %). FT-IR: νmax, cm 3077, 2924, 2854 (C – H); 2230 (C≡N); 1577, 1479, 1420 (C = C ); 1248 (Ar–
ar
ar
ar
1
O–Ar). H NMR (500 MHz, THF-d ): δ, ppm 7.89 (s, 4 H), 7.87 (s, 4 H), 7.56 (dd, J = 8.1, 2.2 Hz, 8 H), 7.50 (t, J = 2.2 Hz,
8
4
H), 7.39 (dd, J = 7.9, 2.2 Hz, 4 H), 7.37 (dd, J =8.1, 2.2 Hz, 4 H), 7.03 (dd, J =8.2, 2.1 Hz, 4 H), 7.01 (dd, J =8.0, 2.2 Hz, 4
+
H), 6.97 (s, 4 H). MS (MALDI-TOF): m/z 1513.15 [M] , calcd. 1512.94. Anal. calcd for C88
N 14.81, O 8.46, Cu 4.20; found: C 69.87, H 2.67, N 14.80, O 8.48, Cu 4.18.
Cu(II) tetrakis-[4-(3,4-dicyanophenoxy)phenoxy]phthalocyaninate (11)
40 16 8
H N O Cu: C 69.86, H 2.67,
-1
Yield 0.112 g (54 %). FT-IR: νmax, cm 3077, 2917, 2853 (C – H); 2233 (C≡N); 1562, 1495, 1483 (C = C ); 1243 (Ar–
ar
ar
ar
1
O–Ar). H NMR (500 MHz, THF-d ): δ, ppm 7.71 (s, 4 H), 7.69 (s, 4 H), 7.25 (d, J = 2.5 Hz, 8 H), 7.21 (d, J = 2.5 Hz, 4 H),
8
+
,
7
.19 (d, J = 2.6 Hz, 4 H), 7.08 (s, 16 H). MS (MALDI-TOF): m/z 1513.05 [M] calcd. 1512.94. Anal. calcd for
C H N O Cu: C 69.86, H 2.67, N 14.81, O 8.46, Cu 4.20; found: C 69.88, H 2.65, N 14.82, O 8.47, Cu 4.18.
8
8
40 16
8
Spectroscopic studies
Spectroscopic studies were carried out for isomolar series of solutions. Calculation of stability constant for MePc-L
molecular complex formation was carried out based on changes of absorption density of solution in range of Q band.
[
[
nL⋅CoPc
]
n
(
1)
K =
s
CoPc
]
⋅
[
L
]
Equilibrium concentration of molecular complex was calculated as:
(
(
A
0
− A
− A
c
)
)
(2)
0
cCoPc⋅L = c
⋅
CoPc
A
0
∞
0
0 c ∞
where cMePс·L – equilibrium concentration of molecular complex, c MePс – initial concentration of macrocycle. A , A and A
–
initial, equilibrium and final values of solution’s optical density of Q band respectively.
Concentration of free ligand was determined according to equation:
(
(
A0 − Ac
A0 − A∞
)
)
(3)
0
L
0
c = c −c
⋅
L
CoPc
Taking into account equations 2 and 3 the formula for calculating stability is to be:
1
5


(
A0 − A
)
/
(
Ac − A
)



c
∞
(4)
K =
s
0
L
0

c −c
⋅
(
A0 − Ac
)
/
(
A0 − A∞

)

CoPc

The investigation was carried out with excess of ligand relative to the metallophthalocyanine. That is why
equilibrium concentration of the ligand is considered to be equal to its initial concentration. It simplifies calculating Ks:
A0 − A
c
(5)
K =
s
0
(
A − A )c
L
0
∞
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)


Ac − A
∞
where c
density respectively
Constants of associate stability (ß) were obtained based on EAS data of two wavelengths (before and after the
L 0 c ∞
– equilibrium concentration of axial ligand, A , A и A – initial, equilibrium and final values of solution’s optical
31
shift) and calculated according to:


∆A ∆A
0,λ
2

[
MPc⋅L⋅MPc]
1
i,
λ
1
(
7)
β
=
=




[
MPc⋅L][MPc] [MPc⋅L] ∆A ∆Ai,λ2

0,λ
1
where
λ
1
– initial wavelength,
λ
2
– wavelength after the shift of absorption maximum, ∆А
0
– maimal change of ptical
density at given wavelength, ∆А
i
– change of optical density at given wavelength and concentration.
ACKNOWLEDGEMENTS
This work was supported by the Russian Science Foundation, the project 17-73-20017.
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2
0

SUPPLEMENTARY MATERIALS
1
H NMR spectra of CoPc2 (5)
1
H NMR spectra of CuPc2 (11
)
2
1

1
H NMR spectra of CuPc1 (10
)
1
H NMR spectra of ZnPc1 (6)
2
2

%Int.
1508.06
100
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
1[c]
800
1000
1200
1400
1600
1800
m/z
2000
2200
2400
2600
2800
3000
MALDI-TOF mass spectra of NiPc1 (8)
%Int.
1508.20
100
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
1[c]
1000
1500
2000
2500
3000
m/z
3500
4000
4500
5000
MALDI-TOF mass spectra of NiPc2 (9)
2
3

%Int.
1513.15
100
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
1[c]
800
1000
1200
1400
1600
1800
m/z
2000
2200
2400
2600
2800
3000
MALDI-TOF mass spectra of CuPc1 (10
)
%Int.
1513.05
100
9
8
7
6
5
4
3
2
1
0
0
0
0
0
0
0
0
0
0
1[c]
800
1000
1200
1400
1600
1800
m/z
2000
2200
2400
2600
2800
3000
MALDI-TOF mass spectra of CuPc1 (11
)
2
4

FT-IR spectra of 4,4'-[1,3-phenylenebis(oxy)]diphthalonitrile (2)
FT-IR spectra of 4,4'-[1,4-phenylenebis(oxy)]diphthalonitrile (3)
2
5

FT-IR spectra of CuPc1 (10
)
FT-IR spectra of ZnPc1 (6)
2
6

1
H NMR of 4,4'-[1,4-phenylenebis(oxy)]diphthalonitrile (3)
1
H NMR of 4,4'-[1,3-phenylenebis(oxy)]diphthalonitrile (2)
2
7

Highlights:
‹
‹
‹
‹
d- metal cyanophenoxy-phthalocyaninates were synthesized and
characterized;
Extra- coordination leads to formation of aggregates close to J- and H-
types;
Fluorescence quantum yields increase under the aggregation processes were
found;
Cobalt complexes accelerate DTC oxidation reaction up to 19 times.