Highly organosoluble metal-free phthalocyanines and metallophthalocyanines: Synthesis and characterization

Article abstract of DOI:10.1002/ejic.200600943

The syntheses and characterization of metal-free and metal-containing (Zn and Ni) derivatives of a symmetrically octa-substituted phthalocyanine derived from 4,5:12,13-bis(4′-tert-butylbenzo)-8,9-(4″,5″- dicyanobenzo)-6,11-ditosyl-6,11-diaza-2,15-dithiacy

Full text of DOI:10.1002/ejic.200600943

FULL PAPER
DOI: 10.1002/ejic.200600943
Highly Organosoluble Metal-Free Phthalocyanines and
Metallophthalocyanines: Synthesis and Characterization
Ahmet Bilgin,*[a] Beytullah Ertem,[b] and Yasar Gök[c]
¸
Keywords: Soluble phthalocyanine / Phthalonitrile / Macrocycles / Nickel / Zinc
The syntheses and characterization of metal-free and metal-
10–10 Scm–1 in vacuo and under atmospheric pressure. The
containing (Zn and Ni) derivatives of a symmetrically octa- extraction abilities of NiPc and detosylated phthalocyanines
substituted phthalocyanine derived from 4,5:12,13-bis(4Ј-
tert-butylbenzo)-8,9-(4ЈЈ,5ЈЈ-dicyanobenzo)-6,11-ditosyl-
6,11-diaza-2,15-dithiacyclohexadeca-4,8,12-triene and CuPc
from 4,5:12,13-bis(4Ј-tert-butylbenzo)-8,9-(4ЈЈ,5ЈЈ-dibromo-
benzo)-6,11-ditosyl-6,11-diaza-2,15-dithiacyclohexadeca-
4,8,12-triene were carried out. Pentanuclear silver(I) and pal-
ladium(II) complexes have also been prepared from nickel(II)
phthalocyaninate derivatives. The prepared phthalocyanines
were semiconducting materials in the range of 10–5 to
were evaluated in chloroform/water by using several heavy-
metal picrates such as Ag+, Cd2+, Cu2+, Hg2+, Pb2+, Pd2+, and
Zn2+. The extraction affinities of NiPc and detosylated
phthalocyanines for Ag+ were found to be the highest in sol-
vent extraction experiments. The new compounds were char-
acterized by using elemental analysis, UV/Vis, FTIR, NMR,
MS spectroscopic data and DTA/TG.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
logs[9–12] or macrobicyclic[13,14] and macrotricyclic[15] moie-
ties to the macrocycles, transition-metal phthalocyanine
complexes and their bridged systems can be made soluble
in common organic solvents, for example chloroform or tol-
uene,[4–6] because these substituents increase the distance
between the stacked phthalocyanines and enable their sol-
vation.[5,16] The tert-butyl group is especially suitable to in-
crease the solubility of phthalocyanines in organic sol-
vents.[5] Heteroatom-functionalized substituents were intro-
duced onto the periphery of the phthalocyanine nu-
cleus.[8–17] These peripheral groups are capable of binding
alkali metal ions and provide donor sites for binding transi-
tion-metal ions, which leads to homo- and heteronuclear
complexes.
Unfortunately, for many applications it is preferable to
have both soluble and symmetric phthalocyanines. With
this idea in mind, we set out to synthesize symmetrical di-
tert-butylphtholonitrile and di-tert-butyl-o-dibromobenzene
derivatives for condensation to very soluble symmetrical
octa-tert-butyl-substituted phthalocyanines in this study.
The electrical conductivities of the phthalocyanines as Au/
MPc/Au sandwiches in vacuo and air atmosphere were ex-
amined. Additionally, the heavy metal extraction properties
of 11 and 14 were investigated.
Introduction
Phthalocyanines have been shown to have very interest-
ing properties coupled with excellent stability to heat, light,
and harsh chemical environments. Their optical and elec-
tronic properties have been exploited in various applications
such as pigments in paints and printing inks, infrared secu-
rity devices, information storage, and computer disk wri-
ting, conducting polymers and photoconductors, catalysts
for oxidation of thiols, disulfides, chemical sensors, and in
photodynamic therapy of cancer.[1,2] Transition-metal-
based phthalocyanines have attracted attention in the areas
of fuel cells, gas sensors, and biosensors.[1,2] Most of these
applications require the use of phthalocyanines in the form
of thin films. Further, it is desirable to have ordered, well-
packed, and oriented molecular layers of phthalocyanines
on various substrates.
Applications of peripherally unsubstituted phthalocyan-
ines are restricted because of their insolubility in common
solvents and water.[3,4] Phthalocyanines own an extended π-
conjugated electron system which allows π stacking (aggre-
gation) between planar macrocycles, provided the distance
between the macrocycles is small.[5] By the peripheral at-
tachment of bulky (e.g. tert-butyl),[6] long-chain groups (e.g.
alkyl or alkoxy),[7] N-tosyl derivatives,[8] crown ether ana-
[a] Department of Science Education, Kocaeli University,
41380-Kocaeli, Turkey
Results and Discussion
Fax: +90-262303-2403
E-mail: abilgin@kou.edu.tr
Synthetic Procedure and Characterization
[b] Department of Chemistry, Karadeniz Technical University,
61080 Trabzon, Turkey
The synthetic routes to 3–10 are summarized in Scheme 1
and 11–14 are summarized in Scheme 2. 1,2-Bis(4-tert-bu-
[c] Department of Chemistry, Pamukkale University,
Kınıklı Campus, 20070 Kınıklı, Denizli, Turkey
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A. Bilgin, B. Ertem, Y. Gök
FULL PAPER
tyl-2-nitrobenzylthio)ethane (3) was prepared by a modified in 62% yield. In this work, we were able to easily obtain
literature[18] procedure by the reaction of 1,2-ethandithiol nitro derivative 3 as a pure solid by simple crystallization,
(1) with 4-tert-butyl-2-nitrobenzyl chloride (2) in methanol whereas Sakata and coworkers[18] obtained an oily product
Scheme 1. Synthesis of metal-free phthalocyanines and metallo(Zn, Cu)phthalocyanines.
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Organosoluble Metal-Free Phthalocyanines and Metallophthalocyanines
FULL PAPER
Scheme 2. Synthesis of nickel phthalocyanine and its derivatives.
after a more exhausting and time consuming column
Diamino derivative 4 was obtained by the reduction of 3
chromatography method. This compound was charac- with 10%Pd/C (palladium activated charcoal), hydrazinium
terized spectroscopically and analytically. The 1H NMR hydrate, and n-butyl alcohol in 78% overall yield. Because
spectrum of 3 showed characteristic signals for Ar–CH2–S this method is more advantageous than the others, we pre-
and SCH2–CH2S protons at δ = 4.20 and 2.70 ppm, respec- ferred this one.[19] The disappearance of the signals for the
tively. The 13C NMR spectrum of this compound also NO2 groups at 1543 and 1340 cm–1 and the appearance of
clearly indicates the presence of expected signals related to the signals of the NH2 groups at 3430–3320 cm–1 and bend-
the above-mentioned groups at δ = 31.90 and 32.45 ppm, ing signals at 1610 cm–1 in the IR spectrum confirmed the
1
respectively. The IR spectrum featured a band at 684 cm–1, formation of amino derivative 4. The H and 13C NMR
which is attributable to the C–S bonds. The EI mass spec- spectra of 4 were very similar to those of precursor com-
trum of this compound exhibited a molecular ion peak at pound 3 except for the signals of the NH2 groups at δ =
m/z = 476.23 [M]+, that also supports the structure.
3.82 and 145.56 ppm, respectively. The EI mass spectrum
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A. Bilgin, B. Ertem, Y. Gök
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displayed the [M]+ parent ion peak at m/z = 416.09, which 1040 cm–1 and 1630 cm–1 that are dedicated to the N–H and
confirms the same structure. C=N bonds in the phthalocyanine core of 8, respectively.
1
Reaction of p-toluenesulfonyl chloride with compound 4 In the H NMR spectrum, a peak at δ = –5.24 ppm, which
in dry pyridine[20] afforded compound 5 in 97.5% yield. The is very characteristic for metal-free phthalocyanines, was
IR spectrum of compound 5 shows the signals related to detected and confirmed the suggested structure. The peak
the tosyl groups at 1343–1140 cm–1 and the N–H groups at related to the CϵN groups in the 13C NMR spectrum of 7
3270–1592 cm–1, which indicates that the tosylation reac- vanished in the case of metal-free phthalocyanine 8. Other
tion was clearly achieved. A molecular ion peak at m/z = 1H- and 13C NMR spectra peaks resembled those of precur-
724.19 [M]+ in its mass spectrum together with elemental sor compound 7. The mass spectrum of 8 was measured as
analysis data clearly supports the structure of compound 5. m/z = 3507.45 [M]+ and is in good accord with the sug-
1
The H NMR spectrum of compound 5 exhibits signals for gested structure.
both the N–H and tosyl groups at δ = 8.29 ppm and δ =
Cyclization of 7 with zinc(II) acetate or nickel(II) chlo-
7.85–7.35 (Tosyl–Ar–H) and 2.32 ppm (Tosyl–CH3), respec- ride in the presence of DBU in n-pentyl alcohol then fur-
tively. The 13C NMR spectrum shows the signals at δ = nished the corresponding (phthalocyaninato)metal com-
148.56 ppm (Ar–C–NH) and 144.62, 135.32, 130.23, plexes 9 or 11. The elemental analysis and mass spectro-
127.44 ppm (Ts–Ar), and 21.34 (Tosyl–CH3), respectively. scopic data of 9 (m/z = 3570.31 [M]+) and 11 (m/z = 3563.15
1
All these spectroscopic data confirm the proposed struc- [M]+) are consistent with their calculated values. The H
ture.
NMR spectra of these compounds were almost identical to
Dibromobenzene derivative 6 was obtained from the re- those of metal-free phthalocyanine 8. The differences in the
action of compound 5 and α,αЈ-dibromomethyl-4,5-dibro- 1H NMR spectra of H2Pc, ZnPc, and NiPc were the broad
mobenzene in 36% yield as a pale brown solid. From the signals encountered in the case of compound 9 and 11 as
IR spectrum, the formation of the C–Br bond was con- a result of the aggregation of phthalocyanine cores at the
firmed by the presence of the peak at 632 cm–1, and the considerable high concentration used for the NMR mea-
signals for the N–H group of compound 5 at 3270– surements.[22] The other characteristics of these compounds
1592 cm–1 disappeared. Other IR peaks are similar to those were quite similar to those of 7 and 8. Cyclotetramerization
of compound 5. The N–H signals observed for compound of 7 was confirmed by the disappearance of the sharp CϵN
1
5 at δ = 8.29 ppm in the H NMR spectrum disappeared stretching vibration at 2224 cm–1 in the IR spectrum. The
and a new peak arose at δ = 7.75 ppm, which results from IR spectra of NiPc and ZnPc are also very similar to that
α,αЈ-dibromomethyl-4,5-dibromobenzene. The 13C NMR of the precursor H2Pc except for the disappearance of the
spectra of 6 was very similar to that of the precursor com- N–H vibration of the phthalocyanine core.
pound 5 except for the carbon signal at δ = 149.41 ppm for
the Ar–C–N– group. MS (FAB positive): m/z = 983.3 [M]+ from dibromo derivative 6, CuCN, and quinoline in 42%
also confirmed the structure. yield. The comparison of the IR spectra obtained from 6
Copper(II) phthalocyanine (10) was synthesized directly
Substitution of the bromo groups in 6 with cyanide moie- and 10 confirmed the conversion of the bromo groups into
ties by a Rosenmund–von Braun reaction with cuprous cya- the characteristic skeleton moiety of phthalocyanine. In this
nide[21] afforded corresponding phthalonitrile 7 in 58% case, the C–Br band at 632 cm–1 disappeared and a C=N
yield. In the IR spectrum of 7, the signal at 632 cm–1 for the stretching vibration at 1642 cm–1 appeared. The mass spec-
C–Br bond vanished and a new peak at 2224 cm–1 appeared trum of 10 showed a peak corresponding to [M + 1]+ at
which was attributed to the dicyano groups. In the 13C m/z = 3568.15.
NMR spectrum of this compound, the presence of the sig-
Metal-free phthalocyanine 8 and metallophthalocyanines
nal at δ = 115.62 ppm, attributable to the nitrile carbon 9–11 and 14 displayed typical UV/Vis electronic spectra
atom, indicated that the conversion had taken place; the 1H with two significant absorption bands, one of them in the
NMR spectrum displayed similarities with that of precursor visible region at about 710–600 nm corresponding to the Q
compound 6. The mass spectrum of compound 7 should a band, and the other in the UV, approximately at 300 nm.
peak at m/z = 876.29 [M]+ and this is in a good accord with The Q band absorptions of 8 in chloroform at λmax = 710,
the suggested structure.
672, and 656 nm and the other absorption at 376 and
Because of the eight tert-butyl and eight tosyl peripheral 310 nm are consistent with the results obtained previously
groups, all phthalocyanines except for 12 and 13 possess for similar phthalocyanines (Figure 1A).[23] The Q band ab-
good solubility in common organic solvents and they can sorption present in 8 can be attributed to the fact that the
be purified by column chromatography by using appropri- symmetry of the metal-free phthalocyanine is nondegener-
ate solvent systems as coeluents that break up the molecular ate (D2h) and is split in a Qx and a Qy peak as shown in the
aggregation and increase the mobility of these compounds spectrum.[24] The bands between 300–500 nm show super-
on silica gel or neutral alumina columns.
imposed bands of phthalocyanine due to the existence of
Metal-free phthalocyanine 8 was synthesized from the re- the Soret band of phthalocyanine (Pc).
action of phthalonitrile derivative 7, dry n-pentyl alcohol,
The UV/Vis absorption spectra of metallophthalocyan-
and a catalytic amount of DBU. According to the IR spec- ines 9 and 10 are given in Figure 1A and 11 and 14 are
trum of 8, the signals for the CϵN groups at 2224 cm–1 for given in Figure 2 in chloroform at room temperature. These
compound 7 disappeared and new peaks appeared at 3320– compounds showed the expected absorptions at the main
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Organosoluble Metal-Free Phthalocyanines and Metallophthalocyanines
FULL PAPER
Figure 2. UV/Vis spectra of 11 (···) (1ϫ10–5 ) and 14 (–··–··) in
chloroform (1ϫ10–5 ).
CHCl3. For these four compounds, plots of the Q-band ab-
sorbance versus concentration (from 2.50ϫ10–7 to
5.80ϫ10–5 molL–1) gave nearly straight lines, which shows
that the compounds follow the Beer–Lambert law. This ob-
servation indicates that the compounds mainly exist in the
monomeric form under the conditions employed. Complex
14, however, is slightly aggregated at higher concentrations
(ca. 10–4 molL–1). This situation can be attributed to an
increase in the intermolecular interaction between the
phthalocyanine units after removing the bulky tosyl groups
in 11.
Nickel(II) phthalocyaninate derivatives of pentanuclear
silver(I) complex 12 and palladium(II) complex 13 were pre-
pared by treatment of 11 with AgNO3 or Pd(CH3COO)2,
respectively. From the IR spectra of products 12 and 13,
Figure 1. A) UV/Vis spectra of 8 (–––), 9 (----) and 10 (-·-·-·) in
chloroform (1 ϫ 10–5 ). B) Plot of the Q-band (624 nm) ab-
sorbance versus concentration (from 2.5ϫ10–7 to 5.80ϫ10–5 ) in
chloroform.
–
the vibrations belonging to the NO3 groups are observed
at 1382 cm–1 and also symmetrical and asymmetrical vi-
brations of the CH3COO– groups are observed at 1580 and
1420 cm–1, respectively, which confirmed the complexation
1
of silver(I) or palladium(II) cations. The H NMR spectra
peaks of the Q- and B bands appearing at λmax = 690, 692, of 12 and 13 show downfield changes in all the chemical
694, 683 nm and 330, 355, 341, 332 nm, respectively. This shifts of the protons in the macrocyclic rings upon complex
result is typical of metal complexes of substituted and un- formation. This can be attributed to the fact that the sil-
substituted Pc with D4h symmetry.[2,25] Although ZnPc (9), ver(I) and palladium(II) cations are strongly coordinated to
CuPc (10), and NiPc (11) have a typical spectral pattern in the N and S atoms in the macrocyclic rings. The chemical
the UV/Vis region for metallophthalocyanines, CuPc, NiPc, shifts assigned to the acetate groups, which were observed
and detosylated 14 showed the new absorption bands at at δ = 2.39 ppm, also confirmed the formation of target
around 400 nm (466, 419, and 460 nm, respectively) in ad- pentanuclear complex 13. The FAB mass spectra of prod-
dition to the B band.[26] These new bands are sometimes ucts 12 and 13, which were recorded in a triflouroacetic
observed, which can be ascribed to metal-to-ligand charge- acid/m-nitrobenzyl alcohol matrix, show peaks at m/z
transfer or ligand-to-metal charge-transfer transitions be- 4244.92 [M + 2]+ and 4242.56 [M]+, and 4461.50 [M + 1]+,
cause metal ions have partially filled d orbitals. Alterna- 4460.02 [M]+, respectively. Elemental analyses of 12 and 13
tively, when the UV/Vis spectra data of 11 and 14 are com- also confirmed the formation of complexes with silver(I) or
pared, the Q bands in the UV/Vis spectra of 14 are shifted palladium(II) ions.
to shorter wavelengths with a decrease in the molar absorp-
tion coefficient as a result of the tendency to undergo aggre- excess LiAlH4 in THF to give complex 14 containing free
gation. amino groups. Comparison of the IR data gives sufficient
The tosyl groups in 11 were removed by treatment with
Because of the eight bulky tert-butyl and eight tosyl sub- support for the proposed structure. The difference between
stituents, these phthalocyanines are expected to be relatively the spectra of tosylated and free amino groups is clear from
nonaggregated in solution. This was confirmed by variable- the presence of SO2 vibrations in 11 at 1140 and 1343 cm–1
concentration UV/Vis studies of compounds 8–11 in and the free N–H stretching vibrations for 14 at 3290 cm–1.
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A. Bilgin, B. Ertem, Y. Gök
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The tosyl groups’ signals observed for compound 11 in the Ͼ 6 Ͼ 10 Ͼ 12 (Table 2). Cu-containing phthalocyanine
1H NMR spectrum disappeared and a new peak appeared 10 was the most rapidly degrading metallophthalocyanine
at δ = 3.21 ppm belonging to the N–H signals in 14. After whereas Zn- and Ni-containing metallophthalocyanine
detosylation, the tosyl groups’ signals in the 13C NMR showed good thermal stability under the working condi-
spectrum of 14 disappeared. The mass spectrum of com- tions. These results are in good agreement with the litera-
pound 14 was 2338.08 [M + Li]+and 2332.14 [M + 1]+. All ture.[32] The DTA thermogram of 12 showed an endother-
these spectroscopic data confirm the proposed structure.
mic peak at 230 °C, which is due to the dissociation of the
The structures of the obtained phthalocyanines were an nitrate groups. The thermal stabilities of 12 and 13 were
Au/MPc/Au sandwich in the configuration commonly used lower than that of compound 11. The thermal stabilities of
for the electrical conductivity measurements.[27] To prepare 12 and 13 indicate that the dopants are rather weakly
the samples, powdered materials were pressed at a load of bound in the macrocyclic cavities because the bulky tosyl
4 tons for 5 min into disk-shaped compacts with a thickness and tert-butyl groups in the macrocyclic ring have a steric
of 0.55–0.62 mm. The a.c. conductivity and parallel capaci- effect.
tance were measured with an Autolab 30 Voltammetry-
The heavy metal binding ability of N–S-macrocyclic
FRA 2 impedance analyzer. The frequency range was units is a well-known property. The binding abilities of the
100 Hz to 1 MHz and the applied amplitude (rms) was heavy metal ions in the N–S-macrocyclic units were esti-
10 mV. The electrical conductivities of the obtained phthalo-
cyanines were measured in a vacuum and under atmos-
pheric pressure. Table 1 shows the a.c. electrical conductivi-
ties of phthalocyanines 8–14. The conductivity values ob-
Table 2. Thermal properties of the polymeric phthalocyanines.
Compound
Dissociation
of NO3
Initial
Main
tained under atmospheric pressure were higher than those
under vacuum for all phthalocyanines probably because of
absorbed oxygen.[27] These values correspond with those for
semiconductive materials as encountered in a number of
substituted phthalocyanine derivatives.[28] Relative to the
conductivities of 11 and 14, detosylated 14 shows a partial
increase in the conductivity that is due to the removal of
the bulky tosyl groups, which prevent the interaction of de-
localized π-electrons on the phthalocyanine planes. Sixteen-
membered diazadithiamacrocyclic substituents are expected
to provide new chances to enhance the stacking of phthalo-
cyanine units whereas their size and donor atoms are ex-
tremely harmonius to bond with transition metal cations in
a 1:1 (metal/macrocycle ring) ratio.[29] Similar to the alkali
metal complexes of analogous crown ether substituted
phthalocyanines, planarity of the phthalocyanine nucleus
will be extended. As a result, interaction of π-electrons will
be achieved to realize charge transport. A.c. conductivities
of nickel(II) phthalocyanine with four silver(I) or palladi-
um(II) cations in the diazadithiamacrocyclic rings indicate
a clear increase in the case of nitrate or acetate counterions.
The thermal properties of the synthesized macrocyclic
compounds were investigated by DTA/TG.[30] Phthalocyan-
ines are resistant to thermal oxidation. The DTA curves
exhibited exothermic changes for all phthalocyanines 8–14
in the region investigated.[31] The initial decomposition tem-
decomposition temp. decomposition temp.
Tmax [°C]
[°C]
[°C]
6
7
8
9
10
11
12
13
14
–
331
348
337
376
324
345
320
350
335
387
415
425
494
428
454
430
443
438
–
–
230
–
Table 3. Heavy metal picrate extractions for 11[a] and 14[a] under
liquid–liquid phase conditions.
Metal ion
Extractabilities of 11 and 14 [%][b] λmax of metal picrate
11
14
[nm]
Ag+
55.62Ϯ0.01
35.41Ϯ0.01
23.48Ϯ0.01
16.33Ϯ0.01
12.46Ϯ0.01
39.80Ϯ0.01
9.54Ϯ0.01
86.23Ϯ0.01
54.36Ϯ0.01
48.54Ϯ0.01
42.27Ϯ0.01
35.67Ϯ0.01
68.98Ϯ0.01
31.73Ϯ0.01
350
362
355
360
354
360
349
Cd2+
Cu2+
Hg2+
Pb2+
Pd2+
Zn2+
[a] Temperature 25 Ϯ 1 °C; aqueous phase (10 mL), [picrate] =
3.0 ϫ 10–3 ; organic phase (chloroform, 10 mL), [host molecule] =
3.0ϫ10–3 . [b] Average and standard deviation for three independent
perature decreased in the order 9 Ͼ 7 Ͼ 11 Ͼ 8 Ͼ 13 Ͼ 14 measurements.
Table 1. Electrical conductivity of the phthalocyanines at room temperature.
Compound
M
Conductivity [Scm–1]
Pellet thickness
[mm]
in air
in vacuo
8
2H
Zn
Cu
7.75ϫ10–9
3.53ϫ10–8
2.74ϫ10–7
1.58ϫ10–7
2.42ϫ10–5
3.50ϫ10–6
6.72ϫ10–7
6.23ϫ10–10
1.64ϫ10–9
2.36ϫ10–8
3.47ϫ10–8
3.15ϫ10–6
3.97ϫ10–7
4.95ϫ10–8
0.60
0.55
0.65
0.60
0.62
0.56
0.60
9
10
11
12
13
14
Ni
Ni·4AgNO3
Ni·4Pd(CH3COO)2
Ni-8Ts
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Organosoluble Metal-Free Phthalocyanines and Metallophthalocyanines
FULL PAPER
for 2 h. The mixture was then cooled down to room temperature,
benzene (100 mL) was added, and the salt was removed by fil-
tration. The solvent was evaporated and methanol (15 mL) was
added to the residue, which was then kept inside the refrigerator
overnight. The yellow crystals were separated by filtration, dried in
vacuo, and then recrystallized from n-butyl alcohol. Yield: 7.3 g
mated by solvent extraction of heavy metal picrates from
the aqueous phase to an organic phase (Table 3). Picrate
was used as the counter anion for all compounds. As de-
picted in Table 3, the highest extraction affinities of 11 and
14 were determined as 55.62 and 86.23% for Ag+, respec-
tively. The extraction affinity of 14 was more than that of
11 for all working cations. This indicates that cations are
able to bind to 14 easier than they can to 11 after the bulky
tosyl groups were removed.
1
(62%). M.p. 139–142 °C. H NMR (200 MHz, CDCl3): δ = 8.01–
7.48 (m, 6 H, Ar-H), 4.20 (s, 4 H, Ar-CH2-S), 2.70 (t, 4 H, -SCH2-
CH2S-), 1.32 [s, 18 H, (CH3)3C-] ppm. 13C NMR (50 MHz,
CDCl3): δ = 149.5 (Ar-C-NO2), 147.2, 128.2, 124.3, 119.3, 117.2,
34.1 [Ar-C-(CH3)3], 32.5 (S-CH2-CH2-S), 31.9 (Ar-CH2-S), 30.6 [(-
CH ) ] ppm. IR (KBr): ν = 3043 (CH aromatic), 2954–2849(CH
˜
3 3
2
aliphatic), 1543, 1340 (NO2), 684 (C–S) cm–1. MS (EI): m/z =
477.01 [M + 1]+, 476.23 [M]+, 475.30, 285.12, 284.07, 193.24,
192.15 [M – C13H18NO2S2]+. C24H32N2O4S2 (476.12): calcd. C
60.49, H 6.72, N 5.88, S 13.47; found C 60.32, H 6.92, N 5.69, S
13.62.
Conclusions
In this paper, we have described the synthesis and charac-
terization of new very soluble octa-substituted metal-free
phthalocyanines and metallophthalocyanines (M = 2 H,
Zn, Cu, and Ni) by using proper materials. Zn- and Ni-
containing phthalocyanines showed good thermal stability
whereas Cu-containing phthalocyanine degraded the most
rapidly. The DTA thermogram of 12 showed an endother-
1,2-Bis(4-tert-butyl-2-aminobenzylthio)ethane (4): 1,2-Bis(4-tert-bu-
tyl-2-nitrobenzylthio)ethane (7.3 g, 153 mmol) was dissolved in n-
butyl alcohol (200 mL) and heated at 80 °C. The temperature was
then adjusted to 60 °C and 10%Pd/C (0.91 g) was added, and the
mic peak at 230 °C, which is due to the dissociation of the reaction mixture was heated at reflux. Hydrazinium hydrate
(30.6 mL) was added dropwise to the reaction mixture over a
period of 30 min. After the addition, the mixture was heated at
reflux for 10 h, and then the reaction was filtered over celite while
it was hot. n-Butyl alcohol was removed under reduced pressure,
and methanol (25 mL) was added to the residue, which was then
kept in the refrigerator overnight. The precipitated white crystals
were filtered off and washed several times with petroleum ether
nitrate groups. Also, the thermal stabilities of 12 and 13
were lower than that of compound 11. The electrical con-
ductivities of the obtained phthalocyanines were found to
be 10–10–10–5 Scm–1 in vacuo and air. The extraction abili-
ties of 11 and 14 were evaluated by using a solvent extrac-
tion technique and the highest extraction affinities were ob-
served for Ag+ for all working conditions. The extraction
affinity of 14 was more than that of 11 for all working cat-
ions.
1
and dried in vacuo. Yield 3.5 g (78%). M.p. 106–108 °C. H NMR
(200 MHz, CDCl3): δ = 7.29–6.56 (m, 6 H, Ar-H), 3.82 (br. s, 4
H, -NH2), 3.62 (s, 4 H, Ar-CH2-S), 2.91 (t, 4 H, -SCH2-CH2S-),
1.29 [s, 18 H, (CH3)3C-] ppm. 13C NMR (50 MHz, CDCl3): δ =
145.6 (Ar-C-NH2), 143.2, 127.1, 123.3, 118.8, 116.5, 34.0 [Ar-C-
(CH3)3], 31.6 (S-CH2-CH2-S), 30.8 (Ar-CH2-S), 30.2 [(-CH3)3]
Experimental Section
ppm. IR (KBr): ν = 3430–3320 (NH ), 3025 (C–H aromatic), 2965–
˜
2
Materials: Reactions were performed under an atmosphere of ar-
gon. 4-tert-Butyl-2-nitrobenzyl chloride (2) was prepared according
to the literature.[18] All other reagents and solvents were of reagent
grade quality, purchased from commercial suppliers, and they were
dried before use as described in the literature.[33] Silica gel (70–
230 mesh) and Merck 90 active neutral alumina were used for chro-
matographic separations.
2864 (CH2 aliphatic), 1610 (NH2, bending), 1512, 1450, 1234 and
670 (C–S) cm–1. MS (EI): m/z = 417.23 [M + 1]+, 416.09 [M]+,
254.15, 163.17 [M + 1 – C13H20NS2]+, 162.08 [M – C13H20NS2]+.
C24H36N2S2 (416.12): calcd. C 69.21, H 8.65, N 6.73, S 15.40;
found C 68.97, H 8.54, N 6.86, S 15.65.
1,2-Bis(4-tert-butyl-2-tosylaminobenzylthio)ethane (5): p-Tolu-
enesulfonyl chloride (1.233 g, 6.47 mmol) in pyridine (2.5 mL) was
added dropwise over a period of 2 h to a –10 °C solution of 1,2-
bis(4-tert-butyl-2-aminobenzylthio)ethane (3; 1.344 g, 3.23 mmol)
in pyridine (2.5 mL). The reaction was stirred overnight at –10 °C
and then stirred at room temperature for 15 h under a nitrogen
atmosphere. The reaction mixture was gently poured into ice (50–
100 g), conc. HCl (6 mL) was added, and the mixture stirred for
24 h. The precipitated solid was filtered off and washed several
times with deionized water until the washing solvent was neutral.
The pale yellow solid product was then dried in vacuo and recrys-
tallized from acetone. Yield 2.28 g (97.5%). M.p. 220–222 °C. 1H
NMR (200 MHz, CDCl3): δ = 8.29 (s, 2 H, N-H), 7.85 (d, 4 H,
Tosyl-Ar-H), 7.35 (d, 4 H, Tosyl-Ar-H), 6.40–6.98 (m, 6 H, Ar-H),
3.67 (s, 4 H, Ar-CH2-S), 2.73 (t, 4 H, -SCH2-CH2S-), 2.32 (s, 6 H,
Tosyl-CH3), 1.27 [s, 18 H, (CH3)3C-] ppm. 13C NMR (50 MHz,
CDCl3): δ = 148.6 (Ar-C-NH), 144.6 (Ts-Ar), 143.4, 135.3 (Ts-Ar),
130.2 (Ts-Ar), 127.4 (Ts-Ar), 127.2, 123.4, 118.9, 116.2, 34.1 [Ar-
C-(CH3)3], 31.3 (S-CH2-CH2-S), 30.6 (Ar-CH2-S), 30.2 [(-CH3)3],
Measurements: Melting points were determined with an electro-
thermal apparatus and are uncorrected. 1H and 13C NMR spectro-
scopic data were recorded with a Varian XL-200 spectrometer and
IR spectra were obtained with a Perkin–Elmer Spectrum One spec-
trometer. Optical spectra in the UV/Vis region were recorded with
a model Shimadzu 1601 UV/Vis spectrometer with the use of 1-cm
pathlength cuvettes at room temperature. The a.c. conductivity was
measured with an Autolab 30 Voltammetry-FRA 2 frequency ana-
lyzer. The frequency range was 100 Hz to1 MHz and the applied
amplitude (rms) was 10 mV. Mass spectra were measured with a
Varian MAT 711 or a Micromass Quatro LC/ULTIMA LC-MS/
MS spectrometer by using triflouroacetic acid/m-nitrobenzyl
alcohol as the matrix. Elemental analyses were determined with a
CHNS-932 LECO instrument. The metal content of the metallo-
phthalocyanines was determined with a Unicam 929 AA spectro-
photometer.
1,2-Bis(4-tert-butyl-2-nitrobenzylthio)ethane (3): 1,2-ethandithiol
(2 mL, 60 mmol), 4-tert-butyl-2-nitrobenzyl chloride (11.35 g,
50 mmol), and methanol (10 mL) were stirred inside a washing bot-
tle at 50 °C while ammonia gas was bubbled through the solution
21.5 (Ar-CH ) ppm. IR (KBr): ν = 3270 (N–H), 3050 (CH aro-
˜
3
matic), 2990–2835(CH2 aliphatic), 1592 (N–H bending), 1343 and
1140 (SO2), 674 (C–S) cm–1. MS (FAB+): m/z: = 725.30 [M + 1]+,
Eur. J. Inorg. Chem. 2007, 1703–1712
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1709

A. Bilgin, B. Ertem, Y. Gök
FULL PAPER
724.19 [M]+, 570.42 [M + 1 – Ts]+, 471.41, 470.12, 415.08 [M + 1 –
2Ts]+, 414.14[M – 2Ts]+. C38H48N2O4S4 (724.24): calcd. C 62.96,
H 6.62, N 3.87, S 17.71; found C 62.74, H 6.40, N 3.73, S 17.85.
Metal-Free Phthalocyanine 8: Under a dry argon atmosphere, a
standard Schlenk tube was charged with phthalonitrile derivative 7
(150 mg, 0.171 mmol), dry n-pentyl alcohol (1.5 mL), and 3–4
drops of DBU, and the mixture was degassed several times. The
reaction mixture was heated at reflux (155 °C) for 16 h, cooled to
room temperature, and diethyl ether (2–3 mL) was added. The pre-
cipitated light green solid product was filtered off and dried. This
product was purified by column chromatography on silica gel
[dichloromethane/methanol (100:1)]. The combined solvents were
evaporated and light green metal-free phthalocyanine 8 was ob-
tained and then dried in vacuo. Yield: 42 mg (28%). M.p. Ͼ300 °C.
1H NMR (200 MHz, CDCl3): δ = 8.06 (s, 8 H, Ar-H), 7.72–6.72
(m, 56 H, Ar-H), 4.78 (s, 16 H, Ar-CH2-N), 3.69 (s, 16 H, Ar-CH2-
S), 2.80 (t, 16 H, -SCH2-CH2S-), 2.48 (s, 24 H, Tosyl-CH3), 1.27 [s,
72 H, (CH3)3C-], –5.24 (br. s, 2 H, N-H) ppm. 13C NMR (50 MHz,
CDCl3): δ = 156.3, 146.4, 143.9, 141.6, 141.0, 137.1, 131.5, 129.4,
128.1, 126.8, 122.2, 119.8, 112.7, 53.1, 34.1, 31.8, 30.3, 29.5, 22.2
4,5:12,13-Bis(4Ј-tert-butylbenzo)-8,9-(4ЈЈ,5ЈЈ-dibromobenzo)-6,11-di-
tosyl-6,11-diaza-2,15-dithiacyclohexadeca-4,8,12-triene (6): A 500-
mL three-necked round-bottomed flask containing anhydrous
DMF (100 mL) and fitted with a condenser was evacuated, refilled
three times with argon gas and connected to a vacuum line. Under
an argon atmosphere, the flask was charged with 5 (2.28 g,
3.15 mmol) and finely ground anhydrous K2CO3 (2.174 g,
15.75 mmol). The reaction mixture was stirred for 1 h at 45 °C.
α,αЈ-Dibromomethyl-4,5-dibromobenzene (1.349 g, 3.15 mmol) in
anhydrous DMF (50 mL) was added dropwise to the reaction mix-
ture over a period of 6 h, and the reaction mixture was heated at
reflux under an argon atmosphere for 6 d. The reaction was moni-
tored by thin layer chromatography [chloroform/petroleum ether
(7:3)]. At the end of this period, the mixture was cooled to room
temperature, filtered, and washed with dry DMF and dichloro-
methane. The filtrate and the washing solvents were combined and
the solvents evaporated to dryness under reduced pressure. The res-
idue was added to ice (100 g) and stirred for 1 d. Thus, a pale brown
solid was obtained and washed with deionized water (50 mL) and
then dried in vacuo. The final purification of the product was car-
ried out by column chromatography on silica gel (chloroform) to
ppm. IR (KBr): ν = 3320 (N–H), 3054 (CH aromatic), 2963–2874
˜
(CH2 aliphatic), 1630 (C=N), 1510, 1480, 1340 and 1150 (SO2),
1040 (N–H), 750, 680 (C–S) cm–1. UV/Vis (CHCl3): λmax (logε) =
710 (5.34), 672 (5.35), 656 (5.19), 624 (5.08), 376 (5.38), 310 (5.39)
nm. MS (FAB+): m/z = 3507.45 [M]+. C192H210N16O16S16
(3506.96): calcd. C 65.70, H 5.99, N 6.39, S 14.63; found C 65.96,
H 5.90, N 6.57, S 14.97.
1
give a pale brown solid. Yield 1.12 g (36%). M.p. 264–265 °C. H
Phthalocyaninato Zinc(II) (9): Under a dry argon atmosphere, a
standard Schlenk tube was charged with phthalonitrile derivative 7
(100 mg, 0.114 mmol), dry n-pentyl alcohol (1.5 mL), Zn(CH3COO)2·
2H2O (6.4 mg, 0.029 mmol), and 3–4 drops of DBU, and the mix-
NMR (200 MHz, CDCl3): δ = 7.75 (s, 2 H, Ar-H), 7.57 (d, 4 H,
Tosyl-Ar-H), 7.30 (d, 4 H, Tosyl-Ar-H), 6.51–6.78 (m, 6 H, Ar-H),
4.92 (s, 4 H Ar-CH2-N), 3.71 (s, 4 H, Ar-CH2-S), 2.70 (t, 4 H,
-SCH2-CH2S-), 2.40 (s, 6 H, Tosyl-CH3), 1.22 [s, 18 H, (CH3)3C-] ture was degassed several times. The reaction mixture was heated
ppm. 13C NMR (50 MHz, CDCl3): δ = 149.4 (Ar-C-N-), 144.9 (Ts-
Ar), 142.7, 139.4, 134.7, 130.5, 127.5, 127.0, 125.5, 124.4, 119.7,
at reflux (160 °C) for 15 h, cooled to room temperature, and diethyl
ether (2–3 mL) was added. The precipitated green solid product
117.5, 49.7 (Ar-CH2-N-Ar), 34.3 [Ar-C-(CH3)3], 31.7 (S-CH2-CH2- was filtered off, washed with ethanol, water, and diethyl ether,
S), 31.7 (Ar-CH2-S), 29.3 [(-CH3)3], 21.8 (Ar-CH3) ppm. IR (KBr):
respectively, and then dried. The obtained light green product was
purified by column chromatography on silica gel [dichloromethane/
methanol (100:1)]. The collected solvents were evaporated and light
ν = 3048 (CH aromatic), 2995–2865(CH aliphatic), 1340 and 1145
˜
2
(SO2), 676 (C–S), 632 (C–Br) cm–1. MS (FAB+): m/z = 982.23
[M]+. C46H52Br2N2O4S4 (984.05): calcd. C 56.09, H 5.28, N 2.85, green ZnII phthalocyaninate 9 obtained and then dried in vacuo.
S 13.03; found C 56.39, H 5.47, N 2.63, S 13.41.
Yield 38.7 mg (38%). M.p. Ͼ 300 °C. 1H NMR (200 MHz, CDCl3):
δ = 7.90 (br. s, 8 H, Ar-H), 7.67–6.50 (m, 56 H, Ar-H), 4.70 (s,
16H Ar-CH2-N), 3.63 (s, 16 H, Ar-CH2-S), 2.73 (t, 16 H, -SCH2-
CH2S-), 2.39 (s, 24 H, Tosyl-CH3), 1.22 [s, 72 H, (CH3)3C-] ppm.
13C NMR (50 MHz, CDCl3): δ = 153.1, 145.9, 142.4, 141.1, 139.6,
137.3, 130.5, 129.4, 128.3, 127.0, 122.1, 119.7, 110.6, 52.2, 34.9,
4,5:12,13-Bis(4Ј-tert-butylbenzo)-8,9-(4ЈЈ,5ЈЈ-dicyanobenzo)-6,11-di-
tosyl-6,11-diaza-2,15-dithiacyclohexadeca-4,8,12-triene (7): Com-
pound 6 (3.05 g, 3.1 mmol) in anhydrous DMF (30 mL) and CuCN
(0.95 g, 10.66 mmol) were added to a 250-mL round-bottomed
flask. Under an argon atmosphere, the reaction mixture was gently
heated to 160 °C and stirred for 24 h. The reaction mixture was
then cooled to room temperature, a 25% NH3 solution (150 mL)
was added, and oxygen gas was bubbled through the reaction mix-
ture for 24 h. The precipitated solid was then filtered off and
washed several times with deionized water until the filtrate was
neutral. The pale brown product was dried in vacuo over P2O5. The
crude product was purified by column chromatography on silica gel
[chloroform/petroleum ether/methanol (6:3:1)] to give a pale brown
32.5, 31.3, 29.5, 22.0 ppm. IR (KBr): ν = 3050 (CH aromatic),
˜
2990–2848 (CH2 aliphatic), 1632 (C=N), 1512, 1485, 1341 and 1134
(SO2), 756, 672 (C–S) cm–1. UV/Vis (CHCl3): λmax (logε) = 690
(5.45), 665 (4.90), 627 (4.83), 390 (4.96), 330 (5.07) nm. MS
(FAB+): m/z = 3571.54 [M + 1]+, 3570.31 [M]+, 3506.12 [M + 1 –
Zn]+. C192H208N16O16S16Zn (3570.34): calcd. C 64.53, H 5.83, N
6.27, S 14.37, Zn 1.83; found C 64.28, H 5.69, N 6.43, S 14.61, Zn
1.71.
1
solid. Yield: 1.58 g (58%). M.p. 208–210 °C. H NMR (200 MHz,
Phthalocyaninato Copper(II) (10): A mixture of dibromo derivative
6 (250 mg, 0.254 mmol), CuCN (68.2 mg, 0.762 mmol), and quino-
line (1 mL) was placed in a stoppered Schlenk tube under an argon
CDCl3): δ = 7.90 (s, 2 H, Ar-H), 7.60 (d, 4 H, Tosyl-Ar-H), 7.35
(d, 4 H, Tosyl-Ar-H), 6.56–6.79 (m, 6 H, Ar-H), 4.98 (s, 4 H Ar-
CH2-N), 3.75 (s, 4 H, Ar-CH2-S), 2.74 (t, 4 H, -SCH2-CH2S-), 2.42 atmosphere, gently heated to 205 °C and refluxed for 22 h. The
(s, 6 H, Tosyl-CH3), 1.24 [s, 18 H, (CH3)3C-] ppm. 13C NMR reaction mixture was then cooled to room temperature, ethanol
(50 MHz, CDCl3): δ = 147.2 (Ar-C-N-), 144.4, 142.2, 140.7, 133.7,
130.3, 127.5, 127.0, 124.0, 118.7, 116.3, 115.6 (CϵN), 114.1, 51.1
(10 mL) added, stirred for 15 min, and filtered. The solid product
was heated with a 3  NaCN solution (3ϫ25 mL) in order to re-
(Ar-CH2-N-Ar), 35.0 [Ar-C-(CH3)3], 32.9 (S-CH2-CH2-S), 32.5 move excess CuCN over a period of 5 h. The dark green residue
(Ar-CH -S), 30.1 [(-CH ) ], 20.9 (Ar-CH ) ppm. IR (KBr): ν = was filtered off and dried. This product was charged into a Soxhlet
˜
2
3 3
3
3045 (CH aromatic), 2980–2854(CH2 aliphatic), 2224 (CϵN), 1500,
1460, 1343 and 1148 (SO2), 675 (C–S) cm–1. MS (FAB+): m/z =
876.32 [M]+. C48H52N4O4S4 (876.24): calcd. C 65.74, H 5.93, N
6.39, S 14.64; found C 65.44, H 5.68, N 6.64, S 14.02.
extraction column and extracted with chloroform for 18 h. The sol-
vent was removed and solid product obtained. This green CuII
phthalocyanine derivative was purified by column chromatography
on neutral alumina (chloroform) to give a dark green solid product.
1710
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 1703–1712

Organosoluble Metal-Free Phthalocyanines and Metallophthalocyanines
FULL PAPER
Yield 95 mg (42%). M.p. Ͼ 300 °C. IR (KBr): ν = 3060 (CH aro- 1470, 1420 (sym. CH3COO), 1343, 1220, 1110, 1090, 1040, 1010,
˜
matic), 2985–2862 (CH2 aliphatic), 1642 (C=N), 1515, 1495, 1350 740, 674 cm–1. MS (FAB+): m/z = 4461.50 [M + 1]+, 4460.02
and 1138 (SO2), 755, 673 (C–S) cm–1. UV/Vis (CHCl3): λmax (logε) [M]+, 4400.13 [M – CH3COOH]+. C208H232N16NiO32Pd4S16
= 692 (5.26), 655 (4.73), 611 (4.66), 466 (4.75), 394 (5.20), 355 (5.38) (4461.26): calcd. C 55.95, H 5.20, N 5.02, S 11.50, Ni 1.32, Pd 9.54;
nm. MS (FAB+): m/z = 3568.15 [M + 1]+, 3504.72 [M + 1 – Cu]+. found C 56.14, H 5.32, N 4.87, S 11.65, Ni 1.49, Pd 9.75.
C192H208CuN16O16S16 (3568.42): calcd. C 64.57, H 5.83, N 6.28, S
14.37, Cu 1.78; found C 64.74, H 6.03, N 6.49, S 14.85, Cu 1.94.
Detosylation of 11 with LiAlH4 – Compound 14: A solution of 11
(0.100 g, 0.028 mmol) in dry THF (100 mL) was slowly added to a
stirred suspension of LiAlH4 (0.11 g, 2.8 mmol) in dry THF
(100 mL) at room temperature under an argon atmosphere. The
resulting mixture was stirred and heated at reflux for 5 d. A mixture
of ethyl acetate and water was carefully added with stirring at 0 °C
Phthalocyaninato Nickel(II) (11): Dicyano derivative 7 (80 mg,
0.091 mmol), dry n-pentyl alcohol (1.5 mL), NiCl2 (12 mg,
0.092 mmol), and 3–4 drops of DBU were placed into a standard
Schlenk tube under a dry argon atmosphere, and reaction mixture
to decompose the excess LiAlH4. The resulting precipitate was fil-
was evacuated several times and refilled with dry argon. Under an
tered and washed thoroughly with ethyl acetate and CH2Cl2. The
argon atmosphere, the reaction mixture was heated at reflux
(155 °C) for 18 h. The reaction mixture was then cooled to room
temperature, filtered, and dried. The obtained product was purified
combined filtrates were dried (MgSO4) and the solvents evapo-
rated. The residue was purified by chromatography on silica gel
[CH2Cl2/CH3OH/NH4OH (98:1:1)]. Evaporation of the solvent
by column chromatography on silica gel [chloroform/methanol
gave 14 as a green solid. Yield: 0.016 g (25%). 1H NMR (200 MHz,
(100:1)]. The combined solvents were evaporated and dark green
CDCl3): δ = 7.94 (br., 8 H, Ar-H), 7.17–6.59 (m, 24 H, Ar-H), 4.69
NiII phthalocyaninate 9 was obtained and dried in vacuo. Yield
1
(s, 16H Ar-CH2-N), 3.65 (s, 16 H, Ar-CH2-S), 3.21 (br. s, 8 H, N-
H, D2O exchange), 2.78 (t, 16 H, -SCH2-CH2S-), 1.24 [s, 72 H,
(CH3)3C-] ppm. 13C NMR (50 MHz, CDCl3): δ = 152.6, 150.1,
147.8, 139.4, 136.3, 127.8, 123.8, 122.6, 118.5, 112.3, 45.6, 34.0,
26.5 mg (32.6%). M.p. Ͼ 300 °C. H NMR (200 MHz, CDCl3): δ
= 7.93 (br. s, 8 H, Ar-H), 7.68–6.54 (m, 56 H, Ar-H), 4.73 (s, 16H
Ar-CH2-N), 3.61 (s, 16 H, Ar-CH2-S), 2.77 (t, 16 H, -SCH2-CH2S-),
2.42 (s, 24 H, Tosyl-CH3), 1.20 [s, 72 H, (CH3)3C-] ppm. 13C
NMR (50 MHz, CDCl3): δ = 153.5, 145.6, 142.3, 140.2, 139.9,
137.2, 130.4, 129.3, 128.1, 127.9, 121.6, 119.5, 109.8, 51.2, 35.0,
32.5, 31.1, 28.9 ppm. IR (KBr): ν = 3290 (N–H), 3040 (CH aro-
˜
matic), 2960–2859 (CH2 aliphatic), 1632 (C=N), 1500, 1490, 1240,
1120 (N–H), 760, 672 (C–S) cm–1. UV/Vis (CHCl3): λmax (logε) =
683 (5.33), 658 (4.38), 606 (4.51), 460 (4.80), 379 (5.30), 332 (5.39)
nm. MS (FAB+): m/z = 2338.08 [M + Li]+, 2332.14 [M + 1]+,
2331.16 [M – Li]+. C136H160N16NiS8 (2331.18): calcd. C 70.01, H
6.86, N 9.61, S 11.00, Ni 2.52; found C 70.21, H 6.68, N 9.54, S
11.27, Ni 2.69.
32.5, 31.1, 29.0, 22.1 ppm. IR (KBr): ν = 3057 (CH aromatic),
˜
2981–2856 (CH2 aliphatic), 1645 (C=N), 1505, 1489, 1346 and 1130
(SO2), 762, 678 (C–S) cm–1. UV/Vis (CHCl3): λmax (logε) = 694
(5.38), 668 (4.85), 622 (4.59), 419 (4.90), 341 (5.41) nm. MS
( FA B + ) : m / z = 3 5 6 3 . 1 5 [ M ] + , 3 5 0 5 . 6 2 [ M – N i ] +
.
C192H208N16NiO16S16 (3563.66): calcd. C 64.65, H 5.84, N 6.29, S
14.39, Ni 1.65; found C 64.49, H 6.14, N 6.11, S 14.56, Ni 1.79.
Measurements of Heavy Metal-Binding Properties of 11 and 14: The
extraction properties of 11 and 14 were investigated under liquid–
liquid phase and neutral conditions by using heavy metal picrates
(Ag+, Cd2+, Cu2+, Hg2+, Pb2+, Pd2+, and Zn2+) as substrates and
by measuring with UV/Vis the amounts of metal picrate in the
aqueous phase before and after treatment with the related com-
pounds. Heavy metal picrates were prepared by the mixture of
metal nitrates (4ϫ10–2 ) and picric acid (1.5ϫ10–2 ) in deion-
ized water. We also prepared solutions (3ϫ10–3 ) of related com-
pounds 11 and 14 in dichloromethane. Equal volumes of both
metal picrate solutions and compound solutions were then added
into plastic bottles, kept closed, and shaken for 10 h by a shaker at
25Ϯ1 °C. After shaking, the aqueous phases were separated and
the percent of picrate salt extracted (E%) was determined by UV
spectrophotometry. For each combination of host and metal pic-
rate, the picrate extraction was conducted on three different sam-
ples and the average value of percent picrate extracted, with stan-
dard deviation, was calculated. The picrate extraction results are
presented in Table 3. In the absence of host, blank experiment, no
metal ion picrate extraction was detected. The extractability was
determined on the basis of the absorbance of picrate ions in the
aqueous solutions. The extractability was calculated by using the
equation below:
Silver(I) Complex of 11 (12): Nickel(II) phthalocyanine derivative
11 (0.10 g, 0.028 mmol) was dissolved in tetrahydrofuran/water
(5.1:0.1) in a 100-mL three-necked round-bottomed flask. Silver
nitrate (0.038 g, 0.225 mmol) in the same solvent mixture (5.1:0.1)
was added. The mixture was heated at reflux for 4 h, and a bluish–
green product formed. The product was filtered off and washed
with hot water, hot ethanol, and then diethyl ether. The deep blue
product was then dried with P2O5 in vacuo. Yield: 0.069 g (58%).
1H NMR (200 MHz, CF3COOD): δ = 7.95 (br. s, 8 H, Ar-H), 7.70–
6.52 (m, 56 H, Ar-H), 4.80 (s, 16 H, Ar-CH2-N), 3.69 (s, 16 H, Ar-
CH2-S), 2.84 (t, 16 H, -SCH2-CH2S-), 2.41 (s, 24 H, Tosyl-CH3),
1.21 [s, 72 H, (CH ) C-] ppm. IR (KBr): ν = 3045, 2942, 1615,
˜
3 3
1480, 1382 (NO3), 1340, 1235, 1120, 1100, 1048, 1015, 840, 760,
681 cm–1. MS (FAB+): m/z = 4244.92 [M + 2]+, 4242.56 [M]+,
4180.26 [M – NO3]+, 4118.17 [M – 2NO3]2+, 4056.08 [M – 3NO3]3+
.
C192H208Ag4N20NiO28S16 (4243.14): calcd. C 54.30, H 4.90, N 6.60,
S 12.09, Ni 1.38, Ag 10.17; found C 54.16, H 4.67, N 6.86, S 12.31,
Ni 1.54, Ag 10.42.
Palladium(II) Complex of 11 (13): Metallophthalocyanine 11
(0.10 g, 0.028 mmol) was dissolved in tetrahydrofuran (5 mL) and
a solution of Pd(CH3COO)2 (0.0503 g, 0.2236 mmol) in THF
(5 mL) was added. The color became bluish–green while heated at
reflux for 5 h and then precipitation occurred. The product was
separated by centrifugation and washed several times successively
with hot water, hot ethanol, and then diethyl ether. The bluish–
green product was filtered off and dried with P2O5 in vacuo. Yield:
0.081 g (65%). 1H NMR (200 MHz, CF3COOD): δ = 8.12 (br. s, 8
H, Ar-H), 7.75–6.50 (m, 56 H, Ar-H), 4.79 (s, 16H Ar-CH2-N),
3.70 (s, 16 H, Ar-CH2-S), 2.85 (t, 16 H, -SCH2-CH2S-), 2.43 (s, 24
E(%) = [(Abefore – Aafter)/Abefore]ϫ100
where Abefore is the absorbance in the absence of ligand. Aafter de-
notes the absorbance in the aqueous solution phase after extrac-
tion.
Acknowledgments
H, Tosyl-CH3), 2.39 (s, 24 H, CH3COO), 1.21 [s, 72 H, (CH3)3C-] This study was supported by The Scientific & Technical Research
ppm. IR (KBr): ν = 3055, 2980, 1630, 1580 (asym.CH COO), 1503, Council of Turkey (TUBITAK), Project Number: TBAG-
˜
3
Eur. J. Inorg. Chem. 2007, 1703–1712
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1711

A. Bilgin, B. Ertem, Y. Gök
FULL PAPER
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Published Online: March 6, 2007
1712
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Eur. J. Inorg. Chem. 2007, 1703–1712