Synthesis and properties of sulfo and alkylsulfamoyl substituted Cu II and Ni II phthalocyanines bearing 1-benzotriazolyl and 4-(1-methyl-1-phenylethyl)phenoxy groups Текст научной статьи по специальности «Химические науки»

Фталоцианины

Phthalocyanines

макрогэтэроцмклы

Статья

Paper

http://macroheterocycles.isuct.ru

DOI: 10.6060/mhc140930z

Synthesis and Properties of Sulfo and Alkylsulfamoyl Substituted Cu" and NiII Phthalocyanines Bearing 1-Benzotriazolyl and 4-(1-Methyl-1-phenylethyl)phenoxy Groups

Serafima A. Znoiko,@a Olga B. Akopova,b Natalia V. Bumbina,b Vladimir E. Maizlish,a Gennady P. Shaposhnikov,a and Nadezhda V. Usol'tsevab

Dedicated to the Corresponding member of Russian Academy of Sciences Prof. Oscar I. Koifman

on the occasion of his Anniversary

aResearch Institute ofMacroheterocycles, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia bResearch Institute of Nanomaterials, Ivanovo State University, 153025 Ivanovo, Russia @Corresponding author E-mail: [email protected]

Synthesis of heterosubstituted sulfo and alkylsulfamoyl derivatives of 2,9,16,23-tetrakis(1-benzotryazolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyanines of copper and nickel was carried out. Their spectral and liquid-crystalline properties were studied.

Key words: Phthalocyanines, metal complexes, synthesis, mesomorphism.

Синтез и свойства сульфо- и алкилсульфамоилпроизводных Cun и Nin фталоцианинов с 1- бензотриазолильными и 4-(1-метил-1-фенилэтил)фенокси группами

С. A. Знойко^ О. Б. Акопова,b Н. В. Бумбина* В. Е. Майзлиш^ Г. П. Шапошников^ Н. В. Усольцеваb

НИИ химии макрогетероциклов, Ивановский государственный химико-технологический университет, 153000 Иваново, Россия

ЬНИИ химии наноматериалов, Ивановский государственный университет, 153025 Иваново, Россия @Е-тай: [email protected]

Синтезированы смешанно-замещенные сульфо- и алкилсульфамоилпроизводные 2,9,16,23-тетра(1-бензо-триазолил)-3,10,17,24-тетра[4-(1-метил-1-фенилэтил)фенокси]-фталоцианинов меди и никеля. Изучены их спектральные и мезоморфные свойства.

Ключевые слова: Фталоцианины, металлокомплексы, синтез, мезоморфизм.

Посвящается Член-корреспонденту РАН Оскару Иосифовичу Койфману по случаю его 70-летнего юбилея

Introduction

Design of novel liquid-crystalline (LC) materials is an actual area of study in organic chemistiy.[1"6] Phthalocyanine derivatives are quite interesting objects for such studies and widely used on many fields of science and technology.[7-9] Particularly phthalocyanines with volumetric substituents are very prospective materials for optoelectronic devices due to the ability of glass-like state formation[10] and light absorb-tion in strongly fixed spectrum region.[7] Herewith it is desirably for them to be mesogen at a temperature which is as low as possible. It is achieved by introducing aliphatic chains on phthalocyanine molecule periphery.[5,9] Moreover, possibility to form lyomesophases in binary systems with different solvents is a very important property of this phthalocyanine derivatives.^^ Solubility of this compounds in water is valuable property for their investigation and application. The simplest way for designing water-soluble phthalocyanines is sulfona-tion. As it was previously shown,[12] sulfoderivatives of phthalocyanine have lyotropic mesophase in aqueous media.[7]

It is known[13,14] that benzotriazolyl substituted phtha-locyanines readily form sulfochlorides at room temperature. This makes possible to obtain readily, on the one hand, sulfo derivatives by hydrolisys of sulfochlorides and, on the other hand, alkylsullfamoyl derivatives (sulfonamides) with extended aliphatic chains by reaction of sulfochlorides with alkylamines.

Previously it was found[15] that 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenyl-ethyl)phenoxy]phthalocyanines of copper and nickel without extended aliphatic chains exhibit enantiotropic mesomor-phism and ability of glass-like state preserving texture of mesophase' formation.

Thus, further modification of metal complexes of mesogenic 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy]phthalocya-nine by forming sulfo and alkylsulfamoyl derivatives is of interest for investigation of effect of their structure on liquid-crystalline behavior.

But the synthesis of these phthalocyanine derivatives is complicated. Therefore it is important to assess how

so3H

SO3H

these compounds are promising from the point of view of the appearance of liquid- crystalline properties. Therefore, anticipating the synthesis, design and prognosis of these compounds' mesomorphism was carried out.

Thereby synthesis of water-soluble sulfoderivatives and high organic-soluble sulfonamides of copper and nickel complexes of 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy] phthalocyanines which can form a low-temperature mesophase is relevant.

Therefore, the aim of this work is the prognosis of mesomorphism, synthesis of modified copper and nickel complexes of 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10, 17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy]phthalo-cyanines (compounds with structures 1, 2) and study of their liquid-crystalline properties.

Experimental

UV-Vis spectra of solutions of synthesized phthalocyanines in DMF and chloroform were fixed on HITACHI U-2001 spectrophotometer at a room temperature on the spectral range 325-900 nm. IR spectra were recorded on Avatar 360 FT-IR ESP spectrophotometer at room temperature. NMR B spectra of [D6] DMSO and CDCl3 test solutions of 1b, 2b of TMS internal standard were carried out on «Bruker DRX-500». Elemental analysis was performed on Flash EATM 1112 instrument. Spectral studies and elemental analysis were carried out on the equipment of the Center for Collective Use (Ivanovo, ISUCT).

Phase state of sulfo 1a,b, and octadecylsulfamoyl derivatives 2a,b of phthalocyanine was studied on optical thermal polarization microscope «Leitz Laborlux 12 Pol» with «Mettler FP 82» heating stage. Forming thermotropic and lyotropic mesophases of binary systems of studied compounds with organic solvents (DMF, DMSO, toluelene, CHCl3) and water was investigated on the equipment of the Research Institute of Nanomaterials (Ivanovo, IvSU).

Synthesis of sulfoderivatives of copper and nickel complexes of 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyanines (1a,b). Compounds 4a,b (188 mg, 0.1 mmol) were dissolved in mixture of 2 ml (18 mmol) of chlorosulfonic acid and 2 ml (18 mmol) of thionyl chloride and stirred at a room temperature for 2 h. Further reaction mixture was poured in mixture of ice and NaCl. Obtained precipi-

s02nhc18h37

s02nhc18H37

S03H

H37C18HNC>2S

M = Cu (a), Ni (b)

so2nhc18h37

tate was collected on the Shott filter and dried on desiccator over concentrated H2SO4 at 36 h. Sulfochlorides were extracted by acetone. Finally, the solvent was removed. Then compounds 5a,b were boiled with water until complete dissolution and water was removed. Finally, compounds 1a,b were purified by chromatography (sorbent - silica gel M 60, eluent - DMF). Sulfo derivatives are water-soluble dark-green crowd products, which soluble in water, aqueous solutions of alkalis and ammonia.

Copper complex of 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10, 17,24-tetrakis[4-(1-methyl-1-phenylethyl)-phenoxy]phthalocya-nine (1a) was synthesized by general method from compound 5a. (175 mg, 0.08 mmol, 78% on phthalocyanine 4a). Found, %: C 62.90, N 12.02, H 4.10, S 5.64; C116H84CuN20O16S4; Calculated, %: C 63.16, N 12.70, H 3.84, S 5.81. IR (KBr) v cm-1: 2930, 2860

v ' max

(CH), 1349 (S=O ), 1240 (Ar-O-Ar), 1173 (S=O ), 1100

v 3/7 v unsym7' v /■> \ symm7'

(C-S), 1040 (N=N), 747 (C-N).

Nickel complex of 2,9,16,23-tetrakis(1-benzotriazolyl)-3,10, 17,24-tetrakis[4-(1-methyl-1-phenylethyl)-phenoxy]phthalocyani-ne (1b) was synthesized by general method from compound 5b (180 mg, 0.08 mmol). (187 mg, 0.09 mmol, 82% on phthalocyanine 4b). Found, %: C 62.71, N 12.56, H 4.01, S 5.58; C116H84NiN20O16S4. Calculated, C 63.30, N 12.73, H 3.85, S 5.83. IR (Kir) v cm"1:

max

2920, 2854 (CH3), 1346 (unsymm. S=O), 1237 (Ar-O-Ar), 1170 (symm. S=O), 1107 (C-S), 1042 (N=N), 744 (C-N). 1H NMR ([D6] DMSO, 393 K) 8H ppm (numbering of protons is shown in Scheme 3): 9.49 (s, 4H, SO3H); 8.59 (t, 4H, H1); 8.23 (t, 4H, H3); 8.13 (s, 4H, H2); 8.03 (s, 4H, H6); 7.91 (s, 4H, H4); 7.73-7,77 (m, 8H, H10-11); 7.55-7.57 (m, 4H, H5); 6.88 (m, 8H, H7>8); 1,43 (s, 24H, H9, CH3).

Synthesis of sulfonamides of 2,9,16,23-tetraki(1-benzotriazolyl)3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl) phenoxy]phthalocyanines of copper and nickel (2a,b). Compounds 4a,b (188 mg, 0.1 mmol) were dissolved in mixture of 2 ml (18 mmol) of chlorosulfonic acid and 2 ml (18 mmol) of thionyl chloride and stirred a the room temperature for 2 h. Further reaction mixture was poured in mixture of ice and NaCl. Precipitate obtained was collected on the Shott filter and dried on desiccator over concentrated H2SO4 at 36 h. Sulfochlorides 5a,b were extracted by acetone. Excess (0.22 g, 0.8 mmol) of octadecylamine was added to solution of 5a or 5b in acetone. Reaction mixture was boiled at 60 0C for 1-1.5 h. Control of process was conducted by the completeness of dissolution in chloroform of the sample of the reaction mixture. Finally, acetone was removed. Compounds 2a or 2b were extracted by chloroform. Purification of targeting derivatives of phthalocya-nine was carried out by columnar chromatography (sorbent - silica gel M 60, eluent - chloroform). Products 2a, b are dark-green solids with good soluble on benzene, acetone and chloroform, and poorly soluble on DMF.

Copper complex of 2,9,16,23-tetrakis(1-benzotriazolyl) 3,10,17,23-tetrakis[4-{1-methyl-1-(4-octadecylsulfamoylphenyl) ethyl}phenoxy]phthalocyanine (2a) was synthesized from compound 5a (180 mg, 0.08 mmol) by general method. (256 mg, 0.08 mmol, 80% on phthalocyanine 4a). Found, %:C 71.70, N 10.66, H 7.22, S 4.01; C^H^CuNO^, Calculated, C 70.30, N 10.47, H

' J 188 232 24 12 4' ' ' '

7.28, S 3.99. (C^CuN^O^). IR (KBr) v^ cm-1: 2921, 2852 (CH2, CH3), 3075 (NH), 1615 (def. NHsec), 1346 (S=O acuMM), 1302: (valent, NHsec), 1246 (Ar-O-Ar), n71 (symm. S=O), 1090 (C-S), 1048 (N=N),c 743 (C-N).

Nickel complex of 2,9,16,23-tetrakis(1-benzotriazolyl) 3,10,17,23-tetrakis[4-{1-methyl-1-(4-octadecylsulfamoylphenyl) ethyl}phenoxy]phthalocyanine (2b) was synthesized from 5b (180 mg, 0.08 mmol) by general method. (263 mg, 0.08 mmol, 82% on phthalocyanine 4b). Found, %: C 71.98, N 10.07, H 7.35, S 3.92; C.^KNiNOA, Calculated, C 70.41, N 10.48, H 7.29, S 4.00.

188 232 24 12 4

IR (KBr) vmax cm-1: 2921, 2853 (-CH2, -CH3), 1626 (deform., NHsec.), 1304 (valent NHsec.), 1174 (symm. S=O), 1200 (Ar-O-Ar), 1148c(C-S), 1040 (N=N^752 (C-N). 1H NMR (CDCl3, 393 K) 8H ppm (numbering of protons is shown in Scheme 3): 8.57 (s, 4H, H1); 8.20 (s, 4H, H3); 8.10 (t, 4H, H2); 8.01 (s, 4H, H6); 7.90 (s, 4H, H4); 7,57 (m, 12H, H5-10-11); 6.99 (m, 8H, H7-8); 4.87 (s, 4H, NH); 1,40 (s, 24H, H9, CH3); 2.98, 1.82, 1.65, 1.25 (CH2 in NHC18H37); 0.9 (s, 12H, CH3 in NHCH).

Results and Discussion

This work consists of several logical steps. The possibility for compounds 1a,b and 2a,b to form mesophases was evaluated on the first stage of the investigation. Synthesis of the objects studied was carried out on the second stage. Finally, liquid-crystalline properties of the target compounds 1a,b and 2a,b were experimentally studied and compared with the results of prognosis.

Prognosis of Mesomorphism on Compounds 1a,b and 2a,b

On the first stage design of discotic molecules and prognosis of columnar mesomorphism for compounds 1a,b and 2a,b was performed by method which was previously used for other phthalocyanine derivatives.116,171 This methodology is based on the construction of molecular models of the compounds and analysis of molecular parameters (MP).[18,19] MP

Figure 1. Models of molecule of compounds 1a (a) and 2a (b). Макрогетер0циmbl /Macroheterocycles 2014 7(3) 287-295

are dimensionless quantities which are calculated on the basis of structure of individual molecule of compound investigated. Preliminary construction and optimization of models of molecules 1a,b and 2a,b were carried out by Molecular Mechanic (MM+) method from the HyperChem software package.

Then calculation and analysis of MP was performed by using geometrical characteristics of the compounds, as well as a number of other indicators. Obtained values were compared with classification number (1).

K = 2-8.5; Kc =1-2.6; Kp = 0.2-0.7; K = 0.25-1.00;

M = 0.2-0.8; M = 0.15 -0.80; K = 0.08-0.30 (1)

m 7 r 7 ar v '

K characterizes anisometry of molecule as a whole. Kc and Kp parameters characterize anisometry of central core and periphery of molecule, respectively. Ks indicates the degree of substitution of the central fragment by the peripheral substituents. Mm parameter takes account the mass ratio of the central core and peripheral fragments. Mr parameter takes account the degree of the environment of the central core of the molecule by peripheral substituents. Parameter Kar is proposed to account for the packing density of peripheral substituents. Detailed description of the parameters and their application for predicting of mesomorphism in different compounds are given in works.[16-20] Deviation of each value of the calculated MP from the limiting values of the classification number (1) illustrated the failure of investigated compounds exhibit mesomorphism characteristic for DM. Results of prognosis for 1a,b - 2a,b are shown in Table 1.

Prognosis was positive for sulfoderivatives of phthalocyanine 1a,b, equally probable for alkylsulfamoyl derivative of copper phthalocyanine 2a and negative for nickel complex 2b.

Synthesis

Synthesis of sulfo and alkylsulfamoyl derivatives of 2,9,16,23-tetrakis(1-benzotriaolyl)-3,10,17,24-tetrakis[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyanines of copper and nickel (1a,b, 2a,b) was performed by methods visualized in Schemes 1-3 for verification of results of the prognosis.

Initial metallophthalocyanines 4a,b were synthesized by heating of 4-(1-benzotriazolyl)-5-[4-(1-methyl-1-phe-nylethyl)phenoxy]phthalonitrile (3) with copper or nickel acetate at 190-220 °C (Scheme 1).[21] All physicochemical characteristics of the synthesized compounds 4a,b coincide with previously published data.[21]

Next step was the synthesis of sulfochlorides 5a,b by interaction of metallophthalocyanines 4a,b with mixture of equimolar quantities of thionyl chloride and chlorosulfonic acid at room temperature for 2 h (Scheme 2). Reaction mixture was poured into mixture of ice and NaCl. Precipitate was collected on a Shott filter and thoroughly dried in a desiccator over concentrated sulfuric acid for 3 days.

Subsequently, compounds 5a,b obtained at this stage were extracted with acetone. The solution was filtered for removal of inorganic impurities and then acetone was removed.

Sulfoderivatives 1a,b were obtained by hydrolysis of sulfochlorides 5a,b with 78-82 % (Scheme 3). Compounds

Table 1. Calculated MP and the data of prognosis for substituted phthalocyanines 1a,b and 2a,b.

№ Е , kcal/mol

opt

Molecular parameter

M

M

K

K

K

K

Р

E

1a 263.44 0.45 0.23 0.52 2.49 1.29 0.24 + +

1b 262.99 0.45 0.23 0.52 2.49 1.33 0.24 + -

2a 336.23 0.27 0.14* 0.17* 2.57 1.29 0.08 ± +

2b 328.15 0.27 0.14* 0.17* 1.56' 1.34 0.08 - -

Note: Eopt - optimization energy, Ks = 0.50 for all compounds, P - prognosis of mesomorfism typical for DM; E - result of experiment. MP* value closed to the boundary of classified number (1). MP'value deviated significantly from number (1).

CH3

Scheme 1.

N=N RlC?

---' \ / \

SOCI2 + HSO3CI, 25 °C, 2h NA M N

W 7/N ---V. //

°C,2h N A

J R1O—\ "7

n-n N^/ \

N=N

5a, b

\\ ^ ta,u _fi

M = Cu (a), Ni (b), R = Rl =

Scheme 2.

5a,b were refluxed in water for complete dissolution and then water was removed.

Sulfonamides 2a,b were synthesized by refluxing of acetone solution of compounds 5a,b and octadecylamine with 80-83 % yield (Scheme 3).

Purification of sulfo (1a,b) and alkylsulfamoyl (2a,b) derivatives of copper and nickel phthalocyanines was carried out by column chromatography.

Synthesized phthalocyanines 1a,b, 2a,b were identified by the data of elemental analysis, NMR 'H, IR and UV-Vis spectroscopy.

According to elemental analysis 4 sulfo or alkylsulfa-moyl groups were entered on the periphery of molecule of compounds 4a,b.

The IR spectra of compounds 1a,b and 2a,b maintain the bands of stretching vibrations of hydroxyaryl (1200-1240

,v M N

V y/ X «

N N-

M = Cu (a), Ni (b), Ri =

1a, b

Rp —

Rs =

S02CI (5a,b),

9 / 7—SO2OH (1a,b), CH3

S02NHC18H37(2a,b),

Scheme 3.

cm-1) and benzotriazolyl (at 1040-1050 cm-1 and 740-750 cm-1) substituents previously noted[21] in the spectra of their synthetic precursors 4a,b.

Bands of stretching and deformation vibrations of C-S (1090-1110 cm-1) and S=O (1150-1170 cm-1) bonds of sulfonic groups[22] appear in the IR spectra of sulfoderivatives 1a,b. Bands of stretching (1310-1350 cm-1) and deformation (15501650 and 1510 cm-1) vibrations of secondary aminogroups and band at 3050-3150 cm-1 of N-H appear in IR spectra of sulfonamides 2a,b. Bands of symmetric (1160-1180 cm-1) and unsymmetric (1330-1360 cm-1) vibrations of S=O, as well as the band of valence vibrations of the C-S are also observed.

'H NMR spectra of phthalocyanines 1b,2b contained signals of protons of aryloxy (6.90-7.90 ppm), benzotriazolyl (8.20, 7.88, 7.55, 8.00 ppm) fragments and benzene rings (8.57 and 8.10 ppm). The position of these signals did not affect on the introduction of sulfo or alkylsulfamoyl groups into aryloxy substituents of compound 4b. This fact confirms the modification of compounds 4a,b in para-position of phenyl ring of 4-(1-methyl-1-phenylethyl)phenoxy groups because signal of proton in the ortho-position of the aryloxy fragment (key 2 in Scheme 3) is observed practically in the same range (8.13 ppm in spectrum of 1b, 8.10 ppm in spectrum of 2b) as in the spectrum of the starting compound 4b (8.10 ppm).[21] Introduction of sulfogroups into ortho-position relatively the oxygen bridge would result in a noticeable shift of these signal in the 8.30-8.36 ppm region. Shift of signal 2 is not observed in this case.

The signal of sulfo protons of sulfo substituted phthalocyanine 1b appears in low field (9.49 ppm) of 1H NMR spectrum. Intensive signals of protons of methylene groups of octadecyl chains of sulfonamide 2b are observed in the upfield region (3.2-1.2 ppm). Signal of four protons of terminal methyl groups are fixed at 0.92 ppm. Singlet signal of protons of secondary aminogroups of octadecylsulfamoyl substituents presents at 4.87 ppm.

Synthesized sulfoderivatives 1a,b are soluble in DMF, water and aqueous-alkaline media, unlike the initial compounds 4a,b. Sulfonamides 2a,b are soluble in organic solvents such as benzene, chloroform and acetone. Results of studies of the electronic absorption spectra of the synthesized phthalocyanine derivatives (1a,b and 2a,b) are summarized in Table 2 and shown in Figures 2-5.

Hypsochromic shift of long-wavelength absorption Q bands in concentrated sulfuric acid is observed at substitution

of aryloxyfragments of 4a, b by sulfogroups (Table 2). This shift is slightly increased at transition from sulfo substituted phthalocyanines 1a,b to sulfonamides 2a,b (Table 2). It should be noted that the nature of Q bands in sulfuric acid under such modification remains unchanged (broad un the case of nickel complexes and cleaved into two parts in the case of copper complexes).

Sulfosubstituted phthalocyanines 1a,b are not associated in DMF media. The position of Q bands of these compounds is identical to that in UV-Vis spectra of their synthetic precursors 4a,b.[21] Additional absorption band (Figure 3) is observed in spectrum of compound 1b in DMF solution and is not observed in water and aqueous-alkaline media. This band was previously fixed[21] in the spectra of other nickel complexes of benzotriazolyl substituted phthalocyanines. It should be noted that compounds 1a,b are in associated form in water and aqueous-alkaline media according to its UV-Vis spectra (Figures 2, 3).

Compounds 2a,b are not associated form in organic solvents (Figures 4, 5). In the spectrum of 2b in DMF an additional absorption band is fixed at 760 nm (Figure 5, Table 2) as in the case of sulfosubstituted phthalocyanine 1b.

Investigation of Mesomorphic Properties of Compounds 1a,b and 2a,b

Liquid crystalline properties of the synthesized compounds 1a,b and 2a,b were studied by method of thermal polarization microscopy. Results of investigation (Table 3, Figures 6-10) were compared with results of prognosis obtained in the analysis of molecular parameters (Table 1).

Sulfosubstituted phthalocyanine 1a is able to form ly-otropic mesophase in binary system with dimethylsulfox-ide (Figure 7) at heating and to form thermotropic meso-phase at 183-227 0C in heating cycle and at 209-184 0C in cooling cycle.

Thus, substitution of aryloxy groups of compound 4a by sulfo group does not lead to the disappearance of mesogenic properties and leads to a shift of existence interval of the mesophase of compound 1a in the region of higher temperatures (Table 3). Furthermore, we have found that sulfosubstituted phthalocyanine 1a forms mesophase at heating in binary systems with dimethylsulfoxide (Figure 7).

Nickel complex of this structure 1b does not exhibit mesomorfic properties (Table 3). Thus, the introduction of

Table 2. The data of UV-Vis spectra of 1a,b and 2a,b.

№ Substituent UV-Vis spectra, X , nm r 7 Max'

H2O NH.OH 4 aaueous DMF H2SO4

1a 1b ,—. chu .—. *--oto- Cu Ni 698 684 648, 693 679 615, 686 684, 668 ' broad 796 803

2a 2b 4a 4b

DMF

CHCl,

R3 =

=\ ch3

ch3 =\ ch3

R =

ch3

s02nhc18H37

|21]

Cu Ni Cu Ni

616,687 613, 682, 767

615, 684 611, 679, 767

618, 689

611, 679, 773 616, 688

612, 676, 774

H2SO4

784 800

805

806

400

500 600 700 800 900

k, nm

400 500 600 700 800 900

X, nm

Figure 2. UV-Vis spectra (1a) in different solvents (C = 0.8-10"5 mol/l): 1 - DMF, 2 - aqueous NH4OH (5%), 3 - H2SO4.

Figure 4. UV-Vis spectra (2a) in different solvents (C = 0.9-10-5 mol/l): 1 - DMF, 2 - CHCl3, 3 - H2SO4.

400

500

600

700

800 900 X, nm

A 1.2-1

1.0

0.8

0.6-|

0.4

0.2-|

0.0

400

500

600

700

800 900 X, nm

Figure 3. UV-Vis spectra (1b) in different solvents (C = 0.7-10-5 mol/l): 1 - DMF, 2 - aqueous NH4OH (5%), 3 - H2SO4.

Figure 5. UV-Vis spectra (2b) in different solvents (C = 1.1-10-5 mol/l): 1 - DMF, 2 - CHCl3, 3 - H2SO4.

Table 3. Liquid-crystalline properties of compounds 1a,b and 2a,b.

№

Substituent

M

Mesomorphism

Thermotropic

Lyotropic

1a 1b 2a

2b

4a[15] 4b[15]

// yp V

ch3

so3h

/=\ CH3 R3 = —( y—I—( s02nhc18h37

n—' ch3

R =

=\ 9H3

ch3

Cu Ni Cu

Ni

Cu

Ni

Heating: Cr ^183,3 °C Mes • 227,1 °C Iso Cooling: Iso ^209,1 °C Mes • 164,5 °C Cr

Heating: Cr • 299,0 0C Iso

Heating: Cr ^108 °C Mes • 197 °C Iso Cooling: Iso ^170°C Mes • 70 °C G

Heating: 170-175 °C - decomposition of amorphous compound

Heating: Cr ^131 °C Mes • 174 °C Iso Cooling: Iso •m °C Mes • 75 °C G

Heating: Cr ^151 °C Mes • 184 °C Iso Cooling: Iso ^175 °C Mes • 114 °C G

DMSO

DMF

sulfo groups into mesogenic molecule of compound 4b is negatively affected on the ability of sulfo derivative 1b to form mesophase.

Observation of sulfonamide samples' texture of 2a in cycles of heating and cooling shows that the mesophase is detected only after several cycles of heating and cooling. This compound shows enantiotropic mesomorphism.

Apparently, multiple heating and cooling cycles are necessary to achieve the thermodynamically stable state. This is probably related with the high viscosity of the sample 2a. Orientational ordering is manifested at shear deformation (Figure 8a-c).

Mobility of the sample increases durning heating. Big domain texture[23] with characteristic spherulites[24] in some

Figure 6. Microscopic image of texture of thermotropic mesophase of compound 1a (heating cycle, crossed polarizers, 218.1 °C).

Figure 10. Glassed mesophase texture of compound 2a, crossed polarizers, 45 °C.

Figure 7. Microscopic image of texture of lyotropic mesophase of compound 1a (contact preparation with DMSO).

areas was shown. This testifies the possible formation of SmA phase (Figure 9a,b).

Sample of compound 2a was glassed upon cooling preserving mesophase texture (Figure 10).

Compound 2a forms mesophase in a wider temperature range than its synthetic precursor 4a. The phase transition Cr ^ Mes of 2a is observed at a significantly lower temperature than that of compound 4a. Apparently this fact is due to increasing of the length of 4-[1-methyl-1-phenylethyl] phe-noxy group at introduction of octadecylsulfamoyl chain.[25]

Influence of the nature of the central metal on mesomorphism of the synthesized compounds is also observed in this case. It was found that nickel phthalocyanine 2b, unlike its synthetic precursor 4b, is non-mesomorphic.

a) Parallel polarizers, 147 °C b) Crossed polarizers (450), 150 °C

Figure 8. Textures of compound 2a during heating cycle.

c) Crossed polarizers (90о), 153 °С

Figure 9. Textures of compound 2a during heating cycle: a) Heating cycle, crossed polarizers, 192 0C, near transition to the isotropic phase; b) Heating cycle, crossed polarizers, 176 °C.

Conclusions

Thus, the sulfo or alkylsulfamoyl derivatives of 2,9,16,23-tetrakis-(1-benzotriazolyl)-3,10,17,24-tetrakis-[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyanines of copper and nickel were synthesized at first time.

Design and prognosis of column mesomorphism characteristic of discotic mesogens for these compounds were held. The results of prognosis were positive for sulfoderivatives 1a,b, equally likely to alkylsulfamoyl substituted copper phthalocyanine 2a, and negative for nickel complex 2b.

Study of UV-Vis spectra of compounds 1a,b and 2a,b shows influence of substitution in 4-(1-methyl-1-phenylethyl)phenoxy fragments on the position of Q bands in spectra in concentrated sulfuric acid. Introduction of sulfo groups causes hypsochromic shift of the Q bands. Replacing of sulfo groups instead of alkylsulfamoyl increases this shift. Position of absorption bands in the organic solvents does not change.

In the study of liquid-crystalline properties of the sulfoderivatives 1a,b a shift of interval of 1a mesophase existence towards higher temperatures was found.

Alkylsulfamoyl derivative 2a shows enanthiotropic mesomorphism. Presence of octadecyl chains in the periphery of 2a causes the decrease in the mesophase transition temperature and significant expansion of the range of existence of liquid-crystalline state in comparison to the parent compound 4a. In addition, the temperature interval of existence of the mesophase alkylsulfamoyl substituted phthalo-cyanines 2a was much wider than that of the corresponding sulfo substituted phthalocyanine 1a. This is probably due to the significant increase of the length of 4-[1-methyl-1-phe-nylethyl]phenoxy fragments by introduction of octadecylsul-famoyl chains.

Acknowledgements. The work was supported mainly by State task for research № 795 (ISUCT, synthesis of compounds), State assignment of RF Ministry of Science and Education № 4.106.2014К (IvSU, prognosis of mesomorphism) and RFBR grant № 13-03-00481a (IvSU, investigation of liquid-crystalline properties).

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Received 15.09.2014 Accepted 11.10.2014