Synthesis and characterisation of new metallophthalocyanines containing four 12-membered diazadithia-macrocyclic moieties

Article abstract of DOI:10.3184/174751912X13472922835683

Tetrasubstituted zinc, cobalt, nickel, copper and lead phthalocyanines bearing four 12-membered diazadithia macrocyclic moieties on peripheral positions have been synthesised by cyclotetramerisation reaction of 1,10-ditosyl-1,2,3,5,6,8,9,10-octahydrobenzo

Full text of DOI:10.3184/174751912X13472922835683

JOURNAL OF CHEMICAL RESEARCH 2012
RESEARCH PAPER 657
NOVEMBER, 657–659
Synthesis and characterisation of new metallophthalocyanines
containing four 12-membered diazadithia-macrocyclic moieties
Elif Çelenk Kayaa*, Halit Kantekinb, Afs¸in Ahmet Kayaa, Asuman Dakog˘lub, Sümeyra Öksüzb
and Hanife S¸is¸ikb
aGümüs¸hane Vocational andTraining School, Gümüs¸hane University, 29100 Gümüs¸hane, Turkey
bDepartment of Chemistry, Faculty of Sciences, KaradenizTechnical University, 61080Trabzon, Turkey
Tetrasubstituted zinc, cobalt, nickel, copper and lead phthalocyanines bearing four 12-membered diazadithia macro-
cyclic moieties on peripheral positions have been synthesised by cyclotetramerisation reaction of 1,10-ditosyl-
1,2,3,5,6,8,9,10-octahydrobenzo[h][1,4,7,10]dithiadiazacyclododecine-12,13-dicarbonitrile and corresponding anhydrous
metal salts under microwave irradiation. The thermal stabilities of the phthalocyanine compounds have determined
by thermogravimetric analysis.
Keywords: phthalocyanine, metallophthalocyanine, macrocyclic compound, mixed-donor macrocyclic, microwave irradiation
Metal porphyrin complexes [MP(-2)] play a vital role in
biological processes such as photosynthesis and respiration.
These complexes have a unique chemistry with several exist-
ing and potential industrial applications. The most commer-
cially important group of the porphyrin class of molecules
is the phthalocyanines, known systematically as tetrabenzo
[5,10,15,20]tetraazaporphyrins.1 Metal phthalocyanines and
their peripherally substituted derivatives have technological
and commercial applications as dyes and printing inks. In
recent decades, there has been renewed interest in the use of
phthalocyanine complexes in high technology fields including
use in semiconductor devices,2 photovoltaic and solar cells,3,4
electrophotography,5 rectifying devices,6 molecular electron-
ics,7 Langmuir–Blodgett films,8,9 electrochromism in display
devices,10 low dimensional metals,11 gas sensors,12,13 liquid
crystals,14 and nonlinear optics,15,9 and as photosensitisers16
and electro catalytic agents.13,17
In photodynamic therapy (PDT), singlet oxygen is gener-
ated using photosensitiser and dioxygen via several energy
transfer steps.18,19 Phthalocyanines are better photosensitisers
for PDT than others, such as porphyrins and naphthalocya-
nines. They exhibit effective tissue penetration because of their
chemical stability, photodynamic activity, and proper light
absorption region. Singlet oxygen has been to cause tumor
necrosis20,21 and also induce several biological reactions.22,23
Nevertheless, the existence of singlet oxygen seems to be
indefinite in the solution. The presence of singlet oxygen is
essential in photodynamic therapy.
Dicyano compound 3 was obtained in 54% yield after being
purified by column chromatography on silica gel using (30%
hexane/ethyl acetate) as eluent. Analytical and spectroscopic
data of 3 clearly confirm the success of the cyclisation reac-
tion. Comparison of their IR spectral data clearly indicate
the formation of compound 3 by the disappearence of the NH
band of compound 1 at 3285 cm−1, and the appearance of a new
absorption at 2233 cm−1 (C≡N). In the 1H NMR spectrum of 3,
the signals belonging to NH protons (δ = 5.33 ppm) in the
precursor compound 3 were absent after the macrocyclisation
reaction.
The 13C NMR spectrum of 3 shows the presence of nitrile
carbon atoms at δ = 115.48 ppm which indicates the comple-
tion of conversion of 1 to 3. FAB mass spectrum and elemental
analysis also confirm the formation of compound 3.
Metallophthalocyanines were obtained from dicyano
derivative 3 and the corresponding anhydrous metal salts
Zn(CH3COO)2, CoCl2, NiCl2, CuCl2, PbCl2 respectively, by
microwave irradiation in 2-(dimethylamino)ethanol in the
range of 10 min. In the IR spectra of metallophthalocyanines,
the disappearance of the strong C≡N stretching vibration of 3
is an evidence for the formation of metallophthalocyanines.
Microwave (MW) irradiation can accelerate a great number
of chemical processes, and, in particular, the reaction time
and energy input are reduced compared with reactions that are
run for a long time at high temperatures under conventional
conditions.24
We have previously desciribed the synthesis and characteri-
sation of some polymeric metal-free and metalophthalo-
cyanines by microwave irradiation.25 We now describe the
synthesis, spectral and thermal characterisation of novel metal-
lophthalocyanines bearing macrocyclic N2S2 donor groups on
peripheral positions.
Results and discussion
Compound 3 was synthesised by the reaction of N,N′-(2,2′-
(ethane-1,2-diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis
(4-methyl benzenesulfonamide) 1 with 1,2-dichloro-4,5-
dicyanobenzene 2 in dry acetonitrile containing finely ground
anhydrous K2CO3 as a template agent at reflux temperature
in a Schlenk system under an N2 atmosphere (Scheme 1).
Scheme 1 The synthesis of the metallophthalocyanines 4, 5,
6, 7 and 8.
Compd
M
4
5
6
7
8
Zn
Co
Ni
Cu
Pb
* Correspondent. E-mail: elifcelenk1629@hotmail.com

658 JOURNAL OF CHEMICAL RESEARCH 2012
In the mass spectrum of compounds 4, 5, 6, 7 and 8, the pres-
ence of molecular ion peaks at m/z= 2516[M]+, 2549[M+K]+,
2532[M+Na]+, 2515[M+1]+, 2659 [M+1]+ respectively, con-
firmed the proposed structures. The elemental analyses also
confirm the proposed formulations.
UV-Vis spectra of the phthalocyanine complexes exhibit
characteristic Q and B bands. The Q-band in the visible region
at 600–750 nm (Q-band) is attributed to the π–π* transition
from HOMO to the LUMO of the Pc(-2) ring, and the B-band
in the UV region at 300–400 nm (B-band) arises from the
deeper π–π* transitions.26
Aggregation is usually depicted as a coplanar association
of rings progressing from monomer to dimer and higher order
complexes. It is dependent on the concentration, nature of the
solvent, nature of the substituents, complexed metal ions and
temperature.27 In this study, the aggregation behaviour of the
phthalocyanine complexes (ZnPc, CoPc and NiPc) were inves-
tigated in different solvents (chloroform, THF and pyridine),
(see Figs 1, 2 and 3). It has been observed that aggregation
increases and the intensity of absorption of the Q band
decreases along with the increase of the solvent polarity.
The thermal behaviour of the metallophthalocyanines were
investigated by TG/DTA. Although the thermal stabilities
of phthalocyanines is well known, these phthalocyanine
compounds are not stable above 208 °C. The initial and main
decomposition temperatures are given in Table 1. The initial
decomposition temperature decreased in the order: 8 > 6 > 7 >
5>.
Conclusion
We have described the synthesis, spectral and thermal
characterisation of novel metallophthalocyanines bearing
macrocyclic N2S2 donor groups on peripheral positions. For
this, N,N′-(2,2′-(ethane-1,2-diylbis(sulfanediyl))bis(ethane-2,1-
diyl))bis(4-methylbenzenesulfonamide) 1 was reacted with
1,2-dichloro-4,5-dicyanobenzene 2 in dry acetonitrile contain-
ing finely ground anhydrous K2CO3 as a template agent to
give compound 3. The metallophthalocyanines 4, 5, 6, 7 and 8
were obtained from dicyano derivative 3 and corresponding
anhydrous metal salts Zn(CH3COO)2, CoCl2, NiCl2, CuCl2,
PbCl2 respectively, by microwave irradiation in 2-
(dimethylamino)ethanol for at 175 °C, 350 W for 10 min. The
thermal stabilities of the metallophthalocyanine compounds
were determined by thermogravimetric analysis.
Fig. 1 UV-Vis spectra of ZnPc (4) in chloroform (―), THF (―),
pyridine (―).
The new macrocyclic compound 3 bearing soft sulfur donor
atoms, moderate soft nitrogen donor atoms and the new metallo
phthalocyanines 4, 5, 6, 7 and 8 containing macrocyclic N2S2
donor groups on peripheral positions might be used in selec-
tive extraction of alkali, alkali earth and transition metal ions.
This field will form an important area of future study.
Experimental
N,N′-(2,2′-(ethane-1,2-diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis
(4-methyl benzenesulfonamide) 1 and 1,2-dichloro-4,5-dicyanoben-
zene 228,29 were prepared according to the reported procedures. All
reactions were carried out under a dry N2 atmosphere using standard
Schlenk techniques. The IR spectra were recorded on a Perkin-Elmer
1
1600 FTIR Spectrophotometer, using potassium bromide pellets. H
and 13C NMR spectra were recorded on a Varian Mercury 200 MHz
spectrometer in CDCl3, and chemical shifts are reported (δ) relative to
Me4Si as internal standard. Mass spectra were measured on a Varian
711 and VG Zapspec spectrometers. Elemental analyses were deter-
mined by a LECO Elemental Analyser (CHNS O932) and Unicam
929 AA spectrophotometer. UV-Vis absorpion spectra were measured
by a Unicam UV-Vis spectrometer. Melting points were measured on
an electrothermal apparatus. A Seiko II Exstar 6000 thermal analyser
was used to record DTA curves under N2 with a heating rate of 20 °C
min−1 in the temperature range 30–900 °C using platinum crucibles.
A domestic oven (Arçelik MD 823, 350 W) was used for all the
synthesis of metallo phthalocyanines.
Fig. 2 UV-Vis spectra of CoPc (5) in chloroform (―), THF (―),
pyridine (―).
Table 1 Thermal properties of the metallo phthalocyanines
Compd
M
İnitial decomposition Main decomposition
Temperature/°C
Temperature/°C
4
5
6
7
8
Zn
Co
Ni
Cu
Pb
219
208
276
268
286
274
268
357
303
318
Fig. 3 UV-Vis spectra of NiPc (6) in chloroform (―), THF (―),
pyridine (―).

JOURNAL OF CHEMICAL RESEARCH 2012 659
Table 2 Some analytical data and physical properties of the
Copper (II) phthalocyanine (7): Yield: 0.057g. (28%), m.p.
>300 °C; νmax (KBr/cm–1) 3071(ArH), 2919–2846 (Aliph.-C–H), 1591
(aromatic–C═C–), 1327, 1259, 1155, 1080, 809, 743. UV-Vis
(CHCl3): λmax / cm−1 707(4.59), 341(5.06), 278(5.26). Anal. Calcd for
C112H112N16O16S16Cu: C, 53.50; H, 4.49; N, 8.91, S, 20.40. Found: C,
53.27; H, 4.14; N, 8.52; S, 19.98%. MS: m/z 2515[M++1].
Lead (II) phthalocyanine (8): Yield: 0.058g. (27%), m.p. >300 °C;
δH (200 MHz, CDCl3) 7.63 (m, ArH, 8H), 7.38 (m, ArH, 32H), 4.38 (t,
J = 6.43 Hz, N–CH2, 16H), 2.63 (t, J = 5.34 Hz, S–CH2, 16H), 2.35 (t,
J = 6.13 Hz, S–CH2, 16H), 1.62 (s, CH3, 24H); νmax (KBr/cm–1)
3065(ArH), 2921–2846 (Aliph.-C–H), 1593(aromatic–C═C–), 1404,
1371, 1156, 1085, 938, 809. UV-Vis (CHCl3): λmax / cm−1 734(4.91),
662(4.49), 344(5.00), 278(5.24). Anal. Calcd for C112H112N16O16S16Pb:
C, 50.61; H, 4.25; N, 8.43, S, 19.30. Found: C, 50.35; H, 4.16; N,
8.50; S, 19.24%. MS: m/z 2659 [M++1].
new compounds
Compd
Empirical
formula
Colour Formula M.p. Yield
wt /°C /%
3
4
5
6
7
8
C28H28N4O4S4
Yellow
612 182–184 54
C112H112N16O16S16Zn Dark green 2516
C112H112N16O16S16Co Dark green 2510
C112H112N16O16S16Ni Dark green 2509
C112H112N16O16S16Cu Dark green 2514
>300
>300
>300
>300
>300
31
33
26
28
27
C112H112N16O16S16Pb Dark green 2658
110-Ditosyl-1,2,3,5,6,8,9,10-octahydrobenzo[h][1,4,7,10 dithiadi-
azacyclodode cine-12,13-dicarbonitrile (3): N,N′-(2,2′-(ethane-1,2-
diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis(4-methylbenzenesulfon-
amide) (1)28 (1.8g., 3.68 mmol) was dissolved in dry acetonitrile
(60 mL), finely ground anhydrous K2CO3 (1.53 g, 11.06 mmol) was
added and the mixture stirred for 2h. at 50 °C. A solution of 1,2-dich-
loro-4,5-dicyanobenzene (2)29 (0.72g, 3.68 mmol) in dry acetonitrile
(30 mL) was added dropwise over 3h. After stirring for 6 days at
reflux temperature, the solvent was removed under reduced pressure,
the residue mixed with water (50 mL) and then extracted with chloro-
form (3×50 mL). The organic layer was dried over anhydrous sodium
sulfate and the solvent was evaporated under reduced pressure to give
an orange-coloured crude product. The product was purified by
column chromatography with silica gel [hexane/ethyl acetate (3:2)].
Finally a yellow solid product (3) was obtained. Compound 3 was
soluble in chloroform, dichloromethane and dimethyl formamide.
Yield: 1.22g. (54%), m.p. 182–184 °C; δH (200 MHz, CDCl3) 8.05 (s,
ArH, 2H), 7.50 (d, J = 7.21 Hz, A part of AB system, Ar-Ts-H, 4H),
7.32 (d, J = 7.21 Hz, B part of AB system, Ar-Ts-H, 4H), 4.14 (t,
J = 5.02 Hz, N–CH2, 4H), 3.94(t, J = 3.91 Hz, S–CH2, 4H), 2.88(t,
J = 4.29 Hz, S–CH2, 4H), 2.43 (s, CH3, 6H); δC (100 MHz, CDCl3)
145.7, 136.1, 131.4, 130.7, 130.3, 127.2, 115.4 (C≡N), 48.5 (N–CH2),
44.9 (S–CH2), 43.4 (S–CH2), 21.9 (CH3); νmax (KBr/cm–1) 3027 (ArH),
2956- 2923 (Aliph.-C–H), 2233 (C≡N), 1713, 1584, 1526, 1483,
1359, 1232, 1163, 1087, 814. Anal. Calcd for C28H28N4O4S4: C, 54.88;
H, 4.61; N, 9.14; S, 20.93. Found: C, 54.44; H, 4.56; N, 9.08; S,
19.82%. MS: m/z 613 [M++1].
This work was supported by The Scientific Technological
Research Council of Turkey (TÜBİTAK Project no: 107T429).
Received 12 August 2012; accepted 30 August 2012
Paper 1201459 doi: 10.3184/174751912X13472922835683
Published online: 12 November 2012
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General procedure for metallophthalocyanine derivates (4–8)
A mixture of compound 3 (0.200 g, 0.327 mmol), anhydrous metal salts
[Zn(CH3COOH)2 (0.015 g, 0.08 mmol), CoCl2 (0.0107 g, 0.08 mmol),
NiCl2 (0.0107 g, 0.08 mmol), CuCl2 (0.0107 g, 0.08 mmol) or PbCl2
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irradiated in a microwave oven at 175 °C, 350 W for 10 min. After
cooling to room temperature the reaction mixture was washed with
hot EtOH–MeOH and dried in vacuo. The solid product was purified
by column chromatography with silica gel [chloroform/methanol
(10: 1) as eluents].
Zinc (II) phthalocyanine (4): Yield: 0.064g. (%31), m.p. > 300 °C;
δH (200 MHz, CDCl3) 7.73 (m, ArH, 8H), 7.56 (m, ArH, 32H), 4.10
(t, J = 6.63 Hz, N–CH2, 16H), 2.43 (t, J = 5.74 Hz, S–CH2, 16H), 2.02
(t, J = 6.13 Hz, S–CH2, 16H), 1.70 (s, CH3, 24H); νmax (KBr/cm–1)
3043 (ArH), 2918–2846 (Aliph.-C–H), 1596 (aromatic–C═C–), 1481,
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/
cm−1 693(5.27), 653(5.03), 350(4.57), 242(5.25). Anal. Calcd for
C
112H112N16O16S16Zn: C, 53.46; H, 4.49; N, 8.90; S, 20.38. Found: C,
53.54; H, 4.38; N, 8.62; S, 19.93%. MS: m/z 2516 [M+].
Cobalt(II) phthalocyanine (5): Yield: 0.068g. (33%), m.p. > 300 °C;
νmax (KBr/cm–1) 3060 (ArH), 2923–2851 (Aliph.-C–H), 1596 (aromatic–
C═C–), 1414, 1345, 1159, 1088, 954, 812, 706. UV-Vis (CHCl3):
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C
112H112N16O16S16Co: C, 53.59; H, 4.49; N, 8.93; S, 20.44. Found: C,
53.66; H, 4.31; N, 8.43; S, 20.54%. MS: m/z 2549 [M++K].
Nickel(II) phthalocyanine (6): Yield: 0.053g. (26%), m.p.: >300 °C;
δH (200 MHz, CDCl3) 7.83 (m, ArH, 8H), 7.38 (m, ArH, 32H), 4.42
(t, J = 6.51 Hz, N–CH2, 16H), 2.56 (t, J = 5.23 Hz, S–CH2, 16H), 2.43
(t, J = 6.02 Hz, S–CH2, 16H), 1.59 (s, CH3, 24H); νmax (KBr/cm–1)
3060 (ArH), 2928–2857 (Aliph.-C–H), 1596 (aromatic–C═C–),
1419, 1349, 1159, 1088, 960, 813, 668. UV-Vis (CHCl3): λmax / cm−1
698(4.71), 632(4.57), 275(5.22). Anal. Calcd for C112H112N16O16S16Ni:
C, 53.61; H, 4.50; N, 8.93; S, 20.44. Found: C, 53.86; H, 4.46; N,
8.34; S, 20.17%. MS: m/z 2532 [M++Na].
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