A new polymeric phthalocyanine containing 16-membered tetrathia macrocyclic moieties by microwave irradiation: Synthesis and characterization

Article abstract of DOI:10.1016/j.jorganchem.2007.12.025

Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile mono

Full text of DOI:10.1016/j.jorganchem.2007.12.025

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 1038–1042
www.elsevier.com/locate/jorganchem
A new polymeric phthalocyanine containing 16-membered
tetrathia macrocyclic moieties by microwave irradiation:
Synthesis and characterization
Halit Kantekin *, Gulsev Dilber, Zekeriya Bıyıklıog˘lu
¨
Department of Chemistry, Faculty of Arts and Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
Received 16 May 2007; received in revised form 11 December 2007; accepted 18 December 2007
Available online 28 December 2007
Abstract
Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1)
onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer with
4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile in 2-(dimethylamino)ethanol. Ni(II),
Co(II), Cu(I)-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II)
and Cu(I) in DMAE. Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetates of
1
Zn(II) in DMAE. The new compounds were characterized by a combination of IR, H NMR, 13C NMR, UV–Vis, elemental analysis
and MS spectral data.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Polymeric phthalocyanine; Bisphthalonitrile; Tetranitrile; Metal-free phthalocyanine
1. Introduction
or water. The solubility can be increased, however, by
introducing alkyl or alkoxy group into the peripheral and
non-peripheral positions of the phthalocyanine framework
[7]. Also phthalocyanines containing thia macrocycles
enhanced the solubility of the product with bulky macrocy-
cles on the periphery.
Compared to the low molecular weight phthalocyanines,
relatively few reports describe the synthesis and properties
of polymeric phthalocyanines. Polymeric phthalocyanines
were mainly prepared via cyclatetramerization reactions
of bifunctional monomers, such as tetracarbonitriles [8,9],
various oxy-, arylenedioxi-, alkylenedioxy-, bridged dipht-
halonitriles [10,11] and other nitriles [12,13] or tetracarb-
oxylic acid derivatives [14,15] in the presence of metal
salts or metals.
In the recent years, a great deal of interest has been
focused on the synthesis of phthalocyanine derivatives due
to their applications in many field such as liquid crystals
[1], chemical sensor [2], non-linear optics [3], gas sensor,
electrochromic devices and photosensitizers. Substituted
phthalocyanine derivatives can also be used for photody-
namic cancer therapy and other processes driven by visible
light [4,5]. The functions of metallophthalocyanine deriva-
tives are almost based on their electron transfer properties
and kinds and number of metal center and substituents
because of their conjugated ring p electron system. Observa-
tion of electron transfer abilities of a compound is a princi-
pal activity for the estimation of functional materials [6].
A decisive disadvantage of phthalocyanine and metal
phthalocyanines is their low solubility in organic solvents
Network phthalocyanine polymers usually possess high
thermal stability [16] and conductivities of semiconducting
polymeric phthalocyanines can be higher than those of the
corresponding low molecular weight phthalocyanines
[17,18]. However, polymeric phthalocyanines can only be
*
Corresponding author. Tel.: +90 462 377 2589; fax: +90 462 325 3196.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.12.025

H. Kantekin et al. / Journal of Organometallic Chemistry 693 (2008) 1038–1042
1039
used in some fields because of their insolubility in water
and common solvents [19].
were recorded with a Unicam UV2-100 spectrophotometer,
using 1 cm pathlength cuvettes at room temperature.
Domestic oven was used for all the syntheses of phthalocy-
anines (see Fig. 1).
The growing use of phthalocyanines as advanced mate-
rials during the last decade has encouraged the research on
the synthesis of newly derivatized materials which differ
from one another in the central metal ion and in the periph-
ery substituents [20]. In addition to the synthetic advantage
in using a linked diphthalonitrile as opposed to a rigid
monomer, such as benzenetetracarbonitrile, in the synthe-
sis of polymeric phthalocyanines is the higher flexibility
of the linkage resulting in a higher group mobility
[10,16,21].
We have previously synthesized phthalocyanines [22–26]
by microwave irradiation. In this paper, we describe the
synthesis and characterization of metal-free phthalocya-
nine polymer (4) and metallophthalocyanine polymers
(5–8) by microwave irradiation containing 16-membered
tetrathia macrocyclic moieties.
2.1. 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-
tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile (3)
1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) (2 g,
6.09 mmol) was dissolved in dry DMF (20 ml) under N2
atmosphere and 4-nitrophthalonitrile (2) (2.10 g, 12.19
mmol) was added to the solution. After stirring for
10 min, finely ground anhydrous K2CO3 (2.52 g, 18.27
mmol) was added portionwise within 2 h with efficient stir-
ring. The reaction mixture was stirred under N2 at 50 °C
for 4 days. Then the solution was poured into ice-water
(200 ml). The precipitate formed was filtered off, washed
first with water until the filtrate was neutral and then with
diethyl ether and dried in vacuo over P2O5. The crude prod-
uct was crystallized from ethanol. Yield: 1.97 g (56%), m.p.:
186–188 °C. Anal. Calc. for C28H28N4O2S4: C, 57.90; H,
4.85; N, 9.65. Found: C, 57.14; H, 4.66; N, 9.69%. IR
(KBr tablet) mmax/cmÀ1: 3071 (Ar–H), 2924–2851 (Aliph.
C–H), 2230 (C„N), 1591, 1561, 1498, 1319, 1256, 1085,
2. Experimental
1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) and
4-nitrophthalonitrile [27,28] (2) were prepared according
to the literature. All reagents and solvents were of reagent
grade quality and were obtained from commercial suppli-
ers. All solvents were dried and purified as described by
Perrin and Armarego [29]. The IR spectra were recorded
on a Perkin–Elmer 1600 FT-IR Spectrophotometer, using
1
989, 845, 525. H NMR. (DMSO-d6), (d: ppm): 8.06 (d,
2H, Ar–H), 7.81 (s, 2H, Ar–H), 7.49 (d, 2H, Ar–H), 4.89
(m, 2H, CH–O), 2.99 (d, 8H, CH2–S), 2.67 (t, 8H, CH2–
S), 1.86 (m, 4H, CH2–CH2–CH2). 13C NMR. (DMSO-d6),
(d: ppm): 160.73, 135.79, 120.95, 120.62, 116.34, 116.02,
115.55, 106.21, 77.79, 33.52, 30.39, 28.95. MS (EI), (m/z):
581 [M+1]+.
1
KBr pellets or NaCl disc. H and 13C NMR spectra were
recorded on a Varian Mercury 200 MHz spectrometer in
CDCl3, DMSO, and chemical shifts were reported (d) rela-
tive to Me4Si as the internal standard. Mass spectra were
measured on a Micromass Quatro LC/ULTIMA LC–
MS/MS spectrometer. Elemental analyses were determined
by a LECO Elemental Analyser (CHNS O932) and an Uni-
cam 929 AA spectrophotometer, respectively. Melting
points were measured on an electrothermal apparatus
and are uncorrected. Optical spectra in the UV–Vis region
2.2. Metal-free polymeric phthalocyanine (4)
A mixture of 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-
1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile
(3) (0.3 g, 0.52 mmol) and 2-(dimethylamino)ethanol
(DMAE) (3 ml) was irradiated in a microwave oven at
2
1.5
1
0.5
0
200
300
400
500
600
700
800
900
λ ( nm )
Fig. 1. UV–Vis spectra of compounds 4 (Á Á Á), 5 (-Á-Á-) and 7 (—) in pyridine.

1040
H. Kantekin et al. / Journal of Organometallic Chemistry 693 (2008) 1038–1042
175 °C, 350 W for 8 min. After cooling to room tempera-
ture, the reaction mixture was refluxed with ethanol
(45 ml) to precipitate the product which was filtered off.
The green solid product was washed with hot ethanol,
diethyl ether and dried in vacuo. This product is soluble
in pyridine. Yield: 110 mg, m.p. > 300 °C. Elemental anal-
yses (for CN end groups) (C112H114N16O8S16)n(2325.19)n
Calc.: C, 57.85; H, 4.94; N, 9.64. Found: C, 57.66; H,
4.02; N, 10.16%. IR (KBr tablet) mmax/cmÀ1: 3281 (N–H),
3071 (Ar–H), 2924–2846 (Aliph. C–H), 2229 (C„N),
1591, 1558, 1488, 1319, 1255 (Ar–O–C), 1084, 845, 527.
UV–Vis (pyridine): kmax/nm: [(10À5 e dm3 molÀ1 cmÀ1)]:
248 (5.13), 332 (4.99), 354 (5.02), 617 (4.57), 683 (5.09),
703 (5.11). MS (FAB), (m/z): 2325 [M]+.
UV–Vis (pyridine): kmax/nm: [(10À5 e dm3 molÀ1 cmÀ1)]:
254 (5.18), 321 (5.11), 344 (5.10), 620 (4.65), 692 (5.24).
MS (FAB), (m/z): 2465 [M+1]+.
2.5. Co(II)-containing polymer (7)
A mixture of 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-
1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile
(3) (0.3 g, 0.52 mmol), anhydrous CoCl2 (16.8 mg, 0.63
mmol) and 2-(dimethylamino)ethanol (DMAE) (3 ml)
was irradiated in a microwave oven at 175 °C, 350 W for
8 min. After cooling to room temperature, the reaction
mixture was refluxed with ethanol (45 ml) to precipitate
the product which was filtered off. The green solid product
was washed with hot ethanol, diethyl ether and dried in
vacuo. This product is soluble in pyridine. Yield: 218 mg,
m.p. > 300 °C. Elemental analyses (for imide end groups)
(C112H116N12O16S16Co)n (2458.12)n Calc.: C, 54.72; H,
4.76; N, 6.84; Co, 2.40. Found: C, 54.11; H, 5.06; N,
6.41; Co, 2.58%. IR (KBr tablet) mmax/cmÀ1: 3423 (imide
N–H), 3082 (Ar–H), 2916–2851 (Aliph. C–H), 1774 (sym.
C@O), 1718 (asym. C@O), 1596, 1472, 1314, 1225 (Ar–
O–C), 1092, 1019, 836, 773. UV–Vis (pyridine): kmax/nm:
[(10À5 e dm3 molÀ1 cmÀ1)]: 261 (5.16), 318 (5.14), 373
(5.11), 614 (4.62), 681 (5.17). MS (FAB), (m/z): 2458 [M]+.
2.3. Ni(II)-containing polymer (5)
A mixture of 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-
1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile
(3) (0.3 g, 0.52 mmol), anhydrous NiCl2 (16.8 mg, 0.13
mmol) and 2-(dimethylamino)ethanol (DMAE) (3 ml)
was irradiated in a microwave oven at 175 °C, 350 W for
8 min. After cooling to room temperature, the reaction
mixture was refluxed with ethanol (40 ml) to precipitate
the product which was filtered off. The green solid product
was washed with hot ethanol, diethyl ether and dried in
vacuo. This product is soluble in pyridine. Yield: 204 mg,
m.p. > 300 °C. Elemental analyses (for imide end groups)
(C112H116N12O16S16Ni)n (2457.87)n Calc.: C, 54.73; H,
4.76; N, 6.84; Ni, 2.39. Found: C, 55.11; H, 5.21; N,
6.02; Ni, 2.56%. IR (KBr tablet) mmax/cmÀ1: 3436 (imide
N–H), 3065 (Ar–H), 2917–2851 (Aliph. C–H), 1775 (sym.
C@O), 1714 (asym. C@O), 1610 (C@N), 1595, 1471,
1314, 1226 (Ar–O–C), 1086, 1055, 946, 837, 524. UV–Vis
2.6. Cu(I)-containing polymer (8)
A mixture of 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-
1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile
(3) (0.3 g, 0.52 mmol), anhydrous CuCl (12.8 mg, 0.13
mmol) and 2-(dimethylamino)ethanol (DMAE) (3 ml)
was irradiated in a microwave oven at 175 °C, 350 W for
8 min. After cooling to room temperature, the reaction
mixture was refluxed with ethanol (45 ml) to precipitate
the product which was filtered off. The green solid product
was washed with hot ethanol, diethyl ether and dried in
vacuo. This product is soluble in pyridine. Yield: 229 mg,
m.p. > 300 °C. Elemental analyses (for imide end groups)
(C112H116N12O16S16Cu)n(2462.73)n Calc.: C, 54.62; H,
4.75; N, 6.82; Cu, 2.58. Found: C, 54.22; H, 5.02; N,
6.19; Cu, 2.68%. IR (KBr tablet) mmax/cmÀ1: 3433 (imide
N–H), 3071 (Ar–H), 2917–2846 (Aliph. C–H), 1770 (sym.
C@O), 1712 (asym. C@O), 1594, 1485, 1316, 1251 (Ar–
(pyridine):
k
max/nm: [(10À5 e dm3 molÀ1 cmÀ1)]: 240
(5.17), 340 (5.07), 362 (5.08), 611 (4.60), 680 (5.16). MS
(FAB), (m/z): 2458 [M+1]+.
2.4. Zn(II)-containing polymer (6)
A mixture of 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-
1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile
(3) (0.3 g, 0.52 mmol), anhydrous Zn(CH3COO)2 (23.8 mg,
0.13 mmol) and 2-(dimethylamino)ethanol (DMAE) (3 ml)
was irradiated in a microwave oven at 175 °C, 350 W for
8 min. After cooling to room temperature, the reaction
mixture was refluxed with ethanol (40 ml) to precipitate
the product which was filtered off. The green solid product
was washed with hot ethanol, diethyl ether and dried in
vacuo. This product is soluble in pyridine. Yield: 220 mg,
m.p. > 300 °C. Elemental analyses (for imide end groups)
(C112H116N12O16S16Zn)n (2464.56)n Calc.: C, 54.58; H,
4.74; N, 6.82; Zn, 2.65. Found: C, 54.71; H, 5.15; N,
6.35; Zn, 2.89%. IR (KBr tablet) mmax/cmÀ1: 3434 (imide
N–H), 3060 (Ar–H), 2920–2851 (Aliph. C–H), 1778 (sym.
C@O), 1711 (asym. C@O), 1614 (C@N), 1595, 1479,
1308, 1251 (Ar–O–C), 1090, 1017, 954, 836, 761, 523.
O–C), 1088, 999, 837, 718, 523. UV–Vis (pyridine): kmax
/
nm: [(10À5 e dm3 molÀ1 cmÀ1)]: 249 (5.14), 320 (5.12), 361
(5.10), 617 (4.57), 689(5.17). MS (FAB), (m/z): 2463
[M+1]+.
3. Results and discussion
Metal-free phthalocyanine polymer (4) and metallopht-
halocyanine polymers (5–8) were synthesized in two steps
(Scheme 1). In the first step, the base-catalyzed nucleophilic
aromatic nitro displacement [30,31] of 4-nitrophthalonitrile
(2) with 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1)
afforded tetranitrile monomer (3). In the second step,

H. Kantekin et al. / Journal of Organometallic Chemistry 693 (2008) 1038–1042
1041
CN
CN
NC
NC
CN
CN
S
S
S
S
i
2
HO
OH
S
S
S
S
O2N
O
O
2
1
3
vi
R
ii
v
iii
iv
R
O
O
S
S
S
S
S
S
S
S
O
O
N
N
N
N
N
N
R
R
N
N
M
N
N
S
S
S
N
M
N
S
S
S
O
O
O
O
N
N
N
S
N
S
C
N
R:
O
R:
N H
Compound
M
4
5
6
7
8
2H Ni Zn
Co Cu
O
i: dry DMF, dry K CO , N ,
50 ºC
3
2
ii: Microwave, 3502W, 4 min, DMAE,
175 ºC
anhydrous NiCl
iii:Microwave, 350 W, 4 min, DMAE, 175 ºC,
2
iv:
Microwave, 350 W, 4 min, DMAE, 175 ºC anhydrous Zn(CH COO)
,
3
2
175 ºC, anhydrous CoCl2
v: Microwave, 350 W, 4 min, DMAE,
vi: Microwave, 350 W, 4 min, DMAE, 175 ºC
, anhydrous CuCl
Scheme 1.
metal-free and metallophthalocyanine polymers were syn-
thesized. The metal-free phthalocyanine (4) was synthesized
by microwave irradiation of the corresponding dicyano
compound 3 in 2-(dimethylamino)ethanol for 8 min. Metall-
ophthalocyanines (5–8) were obtained from tetracyano
derivative 3 and corresponding anhydrous metal salts NiCl2,
Zn(CH3COO)2, CoCl2 and CuCl, respectively, by micro-
wave irradiation in 2-(dimethylamino)ethanol for 8 min.
The molecular weights of the polymers could not be
determined using traditional methods owing to their poor
solubility in organic solvents, but also by comparison of
the IR absorption bands of the end groups with those of
the bridging groups [10,32–36].
In the IR spectrum of 3, the disappearance of NO2 and
OH strecthes, along with the appearance of new bands at
2230 and 1256 cmÀ1 arising from C„N and Ar–O–C
groups, respectively, are in agreement with the proposed
1
structure. In the H NMR spectrum of 3, OH group of
1
compound 1 disappeared as expected. H NMR spectrum
of 3 showed new signals at d = 8.06 (d, 2H, Ar–H), 7.81
(s, 2H, Ar–H), 7.49 (d, 2H, Ar–H), 4.89 (m, 2H, CH–O).
In the 13C NMR spectrum of 3, the presence of nitrile car-

1042
H. Kantekin et al. / Journal of Organometallic Chemistry 693 (2008) 1038–1042
(b) D. Wo¨hrle, M. Kaneko, Yuki Gosei Kagaku Kyokai Shi 45
(1987) 837.
bon atoms in 3 at d116.02 and 115.55 ppm was indicated.
Elemental analysis and EI mass spectral data were satisfac-
tory: 581 [M+1]+.
[3] A. Grund, A. Kaltbeitzel, A. Mathy, R. Schwarz, C. Bubeck, P.
Vernmehren, M. Hanack, J. Phys. Chem. 96 (1992) 7450.
[4] C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines, Properties, and
Applications, vols. 1–4, VCH, New York, 1989, 1993.
[5] M. Hanack, M. Lang, Adv. Mater. 6 (1994) 819.
In the IR spectrum of 4, characteristic peaks for phthal-
ocyanines were observed. The peak at 3281 cmÀ1 is the
characteristic metal-free phthalocyanine N–H stretching
bands. Also, 2229 cmÀ1 (C„N), 1255 cmÀ1 (Ar–O–C)
bands were present in the spectrum. The MS spectrum of
compound 4 displayed the [M]+ parent ion peak at
m/z = 2325, which confirms the same structure. Elemental
analysis was satisfactory.
[6] A. Koca, H.A. Dinßcer, H. C¸ erlek, A. Gul, M.B. Koßcak, Electrochim.
¨
Acta 52 (2006) 1199.
[7] A. Beck, K.M. Mangold, M. Hanack, Chem. Ber. 124 (1991)
2315.
[8] A.A. Berlin, A.I. Sherle, Inorg. Macromol. Rev. 1 (1971) 235.
[9] H. Inoue, Y. Kida, E. Imato, Bull. Chem. Soc. Jpn. 40 (1967)
184.
The IR spectra of the metallophthalocyanine polymers
(5–8) were very similar, except for the metal-free phthalocy-
anine polymer (4) which showed an N–H stretching band at
3281 and 1084 cmÀ1 due to the inner core [37,38]. These
bands disappear in the spectra of the metallophthalocyanine
polymers. These bands are especially beneficial for the char-
acterization of metal-free phthalocyanine polymers, as there
is little frequency dependence on ring substitution and they
are not overlapped by strong bisphthalonitrile monomer
absorptions [16]. The end groups of the metal-free phthalo-
cyanine polymer were cyano groups (2229 cmÀ1) while the
end groups of the metallophthalocyanine polymers were
imido groups (ꢀ1778–1711 cmÀ1). In the mass spectrum
of Ni, Zn, Co, and Cu phthalocyanines, the presence of
molecular ion peaks at m/z = 2458 [M+1]+, 2465 [M+1]+,
2458 [M]+ and 2463 [M+1]+, respectively, confirmed the
proposed structures.
[10] D. Wo¨hrle, B. Schulte, Makromol. Chem. 189 (1988) 1167.
[11] J.A. Hinkley, J. Appl. Polym. Sci. 29 (1984) 3339.
[12] G. Manecke, D. Wo¨hrle, Makromol. Chem. 102 (1967) 1.
¨
[13] A.G. Gurek, O. Bekarog˘lu, J. Porphyr. Phthalocya. 1 (1997) 67.
¨
[14] M. Koß, M. Rohde, Makromol. Chem. 178 (1977) 715.
[15] B.D. Berezin, L.P. Shormanova, Vysokomol. Soedin Ser. A 10 (1968)
338.
[16] D. Wo¨hrle, U. Marose, R. Knoop, Makromol. Chem. 186 (1985)
2209.
[17] D. Wo¨hrle, R. Benters, O. Suvorova, G. Schnurpfeil, N. Trombach,
T. Bogdahn-Rai, J. Porphyr. Phthalocya. 4 (2000) 491.
[18] R.P. Kingsborough, T.M. Swager, Angew. Chem., Int. Ed. 39 (2000)
2897.
[19] F. Cataldo, Dyes Pigments 34 (1997) 75.
[20] C.C. Leznoff, A.B.P. Lever (Eds.), Phthalocyanines, Properties, and
Applications, vol. 4, VCH, New York, 1996.
[21] D. Wo¨hrle, E. Preubner, Makromol. Chem. 186 (1985) 2189.
¨
[22] Z. Bıyıklıog˘lu, H. Kantekin, M. Ozil, J. Organomet. Chem. 692
(2007) 2436.
[23] H. Kantekin, Z. Bıyıklıog˘lu, Dyes Pigments 77 (2008) 98.
[24] Z. Bıyıklıog˘lu, H. Kantekin, Transition Met. Chem. 32 (2007) 851.
[25] H. Kantekin, Z. Bıyıklıog˘lu, Dyes Pigments 77 (2008) 432.
[26] Z. Bıyıklıog˘lu, H. Kantekin, J. Organomet. Chem. 693 (2008) 505.
[27] V.B. Pett, G.H. Leggett, T.H. Cooper, P.R. Reed, D. Situmeang,
L.A. Ochrymowycz, D.B. Rorabacher, Inorg. Chem. 27 (1988)
2164.
The lower solubility of the polymers meant that their
spectra could be obtained in pyridine. The UV–Vis absorp-
tion spectra of these polymers exhibit Q and B bands,
which are the characteristic bands for phthalocyanine
polymers.
There were the split Q-band as expected and there were
two strong bands in the visible region [39]. The split
Q-band, which is characteristic for metal-free phthalocya-
nines observed at kmax = 703 and 683 nm with a shoulder
at 617 nm, indicates the monomeric species with D2h sym-
metry, and shows two intense absorptions at around
700 nm [40,41]. On the other hand, such split Q-band
absorptions in pyridine are due to p–p* transition of this
fully conjugated 18p electron systems [42].
[28] G.J. Young, W. Onyebuagu, J. Org. Chem. 55 (1990) 2155.
[29] D.D. Perrin, W.L.F. Armarego, D.R. Perrin, Purification of
Laboratory Chemicals, second ed., Pergamon Press, New York,
1985.
[30] M. Brewis, G.J. Clarkson, M. Helliwell, A.M. Holder, N.B. McKe-
own, Chem. Eur. J. 6 (2000) 4630.
[31] T.M. Keller, T.R. Price, J.R. Griffith, Synthesis 54 (1980) 2990.
[32] F. Chavez, A.D. Sherry, J. Org. Chem. 54 (1989) 2990.
[33] E. Agar, S. Sasmaz, I. Keskin, N. Akdemir, Dyes Pigments 36 (1998)
249.
[34] A. Bilgin, C¸ . Yag˘cı, U. Yıldız, Macromol. Chem. Phys. 206 (2005)
2257.
Acknowledgement
[35] A. Bilgin, C¸ . Yag˘cı, A. Mendi, U. Yıldız, Polyhedron 26 (2007)
617.
[36] A. Bilgin, A. Mendi, U. Yıldız, Polymer 47 (2006) 8462.
[37] M. Avram, G. Mateescu, Infrared Spectroscpoy, Wiley-Interscience,
New York, 1966, p. 298.
This study was supported by the Research Fund of
Karadeniz Technical University, Trabzon, Turkey.
[38] K. Nakomato, Infrared Spectra of Inorganic and Coordination
Compounds, second ed., Wiley, New York, 1970, p. 325.
References
¨
[39] I. Yılmaz, O. Bekarog˘lu, Chem. Ber. 129 (1996) 967.
[1] (a) C. Piechocki, J. Simon, A. Skouliousi, D. Gullioni, P.J. Weberi,
J. Am. Chem. Soc. 104 (1982) 5245;
[40] O.E. Sielcken, M.M. van Tilborg, R. Hendricks, W. Drenth, R.J.M.
Nolte, J. Am. Chem. Soc. 109 (1987) 4261.
(b) C. Piechocki, J. Simon, Nouv. J. Chim. 9 (1985) 154.
[2] (a) A.W. Snow, W.R. Barger, M. Klusty, H. Wohltjen, N.L. Jarvis,
Langmuir 2 (1986) 513;
[41] E.A. Cuellar, T.J. Marks, Inorg. Chem. 20 (1981) 3766.
_
[42] Y. Go¨k, H. Kantekin, A. Bilgin, D. Mendil, I. Deg˘irmenciog˘lu, J.
Chem. Soc., Chem. Commun. 3 (2001) 285.