Synthesis and characterization of metal-free phthalocyanine containing 16-membered N2S2-donor macrocycles linked to a 2-pyridinyl methyl moiety

Article abstract of DOI:10.1016/j.tetlet.2013.05.125

A metal-free phthalocyanine (H₂Pc) containing four diazadithiamacrocycles a with 2-pyridinyl methyl groups attached was synthesized via cyclotetramerization of 4,5-bis{2-[13(2-pyridinylmethyl)-1,9-dithia-5,13- diazacyclohexadecanyl-5]ethyl} thiophthalonitrile in the presence of DBU as a strong organic base. New compounds were characterized by a combination of elemental analysis, ¹H NMR, ¹³C NMR, IR, UV/vis, and MS spectral data.

Full text of DOI:10.1016/j.tetlet.2013.05.125

Tetrahedron Letters 54 (2013) 4086–4090
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Synthesis and characterization of metal-free phthalocyanine
containing 16-membered N2S2-donor macrocycles linked to a
2-pyridinyl methyl moiety
⇑
Nilgün Kabay, Yaßsar Gök
Department of Chemistry, Pamukkale University, Kınıklı/Denizli, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 20 November 2012
Revised 9 May 2013
Accepted 24 May 2013
Available online 6 June 2013
A metal-free phthalocyanine (H2Pc) containing four diazadithiamacrocycles a with 2-pyridinyl methyl
groups attached was synthesized via cyclotetramerization of 4,5-bis{2-[13(2-pyridinylmethyl)-1,
9-dithia-5,13-diazacyclohexadecanyl-5]ethyl} thiophthalonitrile in the presence of DBU as a strong
organic base. New compounds were characterized by a combination of elemental analysis, 1H NMR,
13C NMR, IR, UV/vis, and MS spectral data.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Metal-free phthalocyanine
Mixed donor macrocycle
Macrocyclization
Detosylation
Pendant arms
Phthalocyanines and related compounds have diverse optical,
electronic, and co-ordination properties and have attracted consid-
erable attention.1 Phthalocyanine chemistry has undergone a
renaissance as these compounds and their derivatives exhibit sin-
gular and unconventional properties. Their interesting applications
include: Langmuir–Blodgett films, electrochromic display devices,
gas sensors, liquid crystals, nonlinear optics, and photodynamic
therapy (PDT).2 Unsubstituted phthalocyanines are colored materi-
als, but they are not generally soluble in common organic solvents.
However, substitution of the peripheral positions of the phthalocy-
anines with appropriate functional groups improves their solubil-
ity and increases their effectiveness in many applications.3 When
functional groups such as sulfonates, carboxylates, and quatern-
ized amino or pyridine groups are attached to the peripheral posi-
tion of the phthalocyanine structure, the solubility of such
compounds can be improved significantly in protic solvents.4
The synthesis of relatively small sized macrocycles such as N4
and S4 donor sets has been well examined.5 In contrast, sulfur
and nitrogen mixed donor macrocycles have been less studied.6
A significant advantage of these types of macrocycles is their abil-
ity to behave as selective metal extraction agents for soft metal
cations such as cadmium, mercury, and silver, and as models for
the active sites of some enzymes.7 N-Functionalization of these
macrocycles may enhance their metal-ion selectivity and the
stability of metal complexes depending on the coordination prop-
erties of the pendant arms. Additionally, macrocyclic complexes
with pendant arms have shown interesting properties as probes
and model molecules in biochemical processes. Metal complexes
with pendant-armed mixed-donor macrocyclic ligands have been
designed as models of electron transport and activation in biolog-
ical systems, and as chemical models of hydrolytic metalloen-
zymes. Such compounds may have various photochemical
applications, for example, the photocatalyzed reduction of CO2
and/or the removal of industrial pollutants like sulfides. Moreover,
N-pyridyl derivatives of macrocyclic compounds and their com-
plexes are soluble in organic media, and they mediate effective
membrane transport of alkaline-earth and some transition metal
cations.8
In our laboratory, we have focused on the synthesis of mixed-
donor macrocycles connected to a tetrapyrrolic skeleton. Consider-
ing that introduction of a pyridine moiety to the macrocyclic back-
bone is expected to increase the stereochemical rigidity of the
resulting complexes, to provide functionalization toward specific
targets, we decided to study a metal-free phthalocyanine in which
are attached 16-membered mixed-donor macrocycles with pen-
dant pyridine moieties. The combination of the two different
groups is expected to result in co-ordination of transition metal
ions (Scheme 1).
Reaction of 2 equiv of 3-chloro-1-propanol (1) and Na2CO3 with
2-(aminomethyl)pyridine (2) in dry acetonitrile at reflux
temperature under a argon atmosphere for five days afforded
⇑
Corresponding author. Tel.: +90 2582963567; fax: +90 2582963535.
E-mail address: gyasar@pau.edu.tr (Y. Gök).
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.05.125

N. Kabay, Y. Gök / Tetrahedron Letters 54 (2013) 4086–4090
4087
Na2CO3, CH3CN
+
2
Ar, 5 d, 85 o
C
N
OH
Cl
N
2
NH2
N
1
HO
OH
3
Thiourea
fuming HCl
Ar, 12 M KOH
I
Cs2CO3, Ar
dry DMF, 40 oC
N
Tos
N
+
N
N
S
N
HS
I
S
SH
N
4
5
Tos
6
LiAlH4, dry THF, Ar
N
N
S
S
N
H
7
Scheme 1. The synthesis of pendant-armed 16-membered mixed donor (N2S2) macrocycle 7.
3,30-(pyridin-2-ylazanediyl)bis(propan-1-ol) (3)9 in ca. 82% yield.
The EI mass spectrum of 3 exhibited a molecular ion peak at m/
z = 225 [M+1]+, which supported the structure. The 1H NMR spec-
trum of 3 showed signals due to aromatic, OCH2, and OH protons
at d 8.41–7.08, d 3.90–3.47, and d 4.82, respectively. The 13C NMR
spectrum of the same compound clearly indicated the presence
of pyridine, pyridine-connected CH2, NCH2, and OCH2 resonances
at d 159.72–123.06, d 52.87, d 60.05, and d 62.19, respectively.
The absence of NH2 and the presence of OH stretching vibrations
in the IR spectrum also confirmed the formation of 3. The conver-
sion of 3 into the mercapto derivative 410 was achieved in 26%
yield by reaction with thiourea and fuming HCl at reflux tempera-
ture for 20 h, followed by cooling to room temperature, dropwise
addition of 12 M KOH solution and then refluxing for 3 h. Product
4 displayed the expected molecular ion peak at m/z = 257 [M+1]+.
In the 1H and 13C NMR spectra of 4, the characteristic resonances
of the aromatic protons and carbons were very similar to those
of 3. The signal at d 2.60 corresponding to the H2C–SH protons
was identified easily by deuterium exchange. The proton-decou-
pled 13C NMR spectrum of this compound showed resonances
due to the H2C–SH groups at d 30.98. The stretching vibrations at
2544 cmꢀ1 representing SH groups in the IR spectrum of this com-
pound also confirmed the formation of 4.
Treatment of 4 with diiodide 511 in dry DMF in the presence of
Cs2CO3 using a high dilution technique resulted in the formation
of the desired diazadithiamacrocycle 612 in 64% yield, the structure
of which was confirmed by elemental analysis and from spectral
data. This compound contained a tosyl moiety as was substantiated
by the two characteristic doublets at d 7.65 and d 7.30 in the 1H NMR
spectrum. The resonances belonging to the SH protons in the pre-
cursor compound 4 were absent after the macrocyclization reaction,
as expected. The molecular ion peak at m/z = 508 [M]+ together with
appropriate ion fragments were in good accord with the suggested
structure. The detosylated macrocycle 713 was prepared in 62% yield
by reaction of 6 with excess LiAlH4. After removal of the tosyl group
from 6, the NH group was observed in the 1H NMR spectrum at d
1.58.6e The proton-decoupled 13C NMR spectrum of this compound
displayed characteristic signals of the product. The disappearance of
the stretching vibration of the tosyl group at 1596 cmꢀ1 and the
presence of N–H absorptions at 3296 cmꢀ1 in the IR spectrum of 7
also confirmed that detosylation had occurred. A molecular ion peak
was observed at m/z = 354.20 [M+1]+ in the mass spectrum.
Macrocycle
7
was reacted with phthalonitrile 814 in the
presence of K2CO3 in refluxing dry acetonitrile to give the corre-
sponding dicyano compound. Purification by column chromatogra-
phy [silica gel (chloroform)] afforded 915 in 68% yield, for which

4088
N. Kabay, Y. Gök / Tetrahedron Letters 54 (2013) 4086–4090
N
S
N
N
N
S
TosO
TosO
CN
CN
S
S
N
K2CO3, dry CH3CN
Ar, 100 oC
CN
CN
S
+
S
S
N
S
S
H
N
N
N
S
8
7
9
N
N
DBU, Ar
n-pentanol
150 oC
N
N
S
S
S
S
N
N
N
S
S
S
S
N
N
N
N
N
N
N
S
S
N
N
S
S
N
N
NH
N
N
N
N
HN
S
S
S
S
S
S
S
N
S
S
N
N
N
S
S
S
N
N
N
N
H2Pc
Scheme 2. Synthesis of the metal-free phthalocyanine (H2Pc).
elemental analysis and ESI mass spectral data were satisfactory:
951.41 [M+1]+. In the IR spectrum of 9, an intense stretching vibra-
tion at 2229 cmꢀ1 corresponded to the C„N groups. A singlet at d
7.53 and multiplet at d 2.77 in the 1H NMR spectrum corresponded
to the tetrasubstituted aromatic group and the SCH2 groups,
respectively. The carbon resonances belonging to the phthalonitrile
group at d 136.36, d 127.48, d 115.41, and d 112.64 were in agree-
ment with the target compound (Scheme 2).
Condensation of four moles of phthalonitrile 9 to give the metal-
free phthalocyanine H2Pc16 was carried out in dry pentanol in the
presence of the nonnucleophilic base, DBU.17 The metal-free phtha-
locyanine was obtained in 11% yield, as a dark green solid, after puri-
fication by column chromatography [silica gel (chloroform)]. In the
IR spectrum of this compound, a diagnostic feature of the formation
of H2Pc from 9 was the disappearance of the sharp C„N signals and
the presence of C@N stretching vibrations at 1641 cmꢀ1. The 1H
NMR spectrum of the symmetric metal-free phthalocyanine exhib-
ited characteristic chemical shifts for the pendant arms and the
macrocyclic moieties. This spectrum closely resembled that of the
precursor 9, as expected. The deuterium exchangeable inner core
protons could not be observed in the 1H NMR spectrum of H2Pc
due to the high aggregation ability of this type of compounds.18 In
the 13C NMR spectrum of H2Pc, a resonance was observed at d
155.27 corresponding to the C@N groups.
cyanine derivative was observed at kmax = 727 and 703 nm due to
an electronic transition from the p
-HOMO to the p⁄-LUMO energy
level.19 This intense Q-bands in compound H2Pc indicated a
monomeric species with D2h symmetry.20 The H2Pc absorption
spectrum showed the expected splitting of the band at 727 and
703 nm, which can be attributed to the monomeric species of this
compound.21 The split Q-band absorptions in chloroform are due
to the
p ? p electron
p⁄ transition of this fully conjugated 18
system.22 The lower energy (red-shifted) band at 670 nm was
due to the monomeric species. The metal-free phthalocyanine
did not show significant aggregation behavior in CHCl3, but it
exhibited a small amount of aggregation in DMF and somewhat
more in DMSO than DMF due to the coordination ability of these
solvents,23 as judged by the broadening and blue-shifting of the
Q band. The presence of strong absorption bands in the UV region
at kma = 347 nm was indicative of the Soret band due to electronic
transitions from deeper
p ?
p⁄ levels.
In conclusion, we have reported the synthesis of metal free
phthalocyanines bearing eight 16-membered N2S2 each with an
N-pyridin-2-ylmethyl substituent. This compound is promising as
selective metal extractant. The synthesized molecule possesses a
versatile funtionalization pattern for further coupling to a wide
range of derivatives. Despite its strong hydrophobicity, it could
be dissolved in water for biological investigations. Based on the
results presented in this Letter, we are now designing metal
extraction studies and related derivatives with improved
hydrophilicity.
The UV/vis absorption spectra of a solution of H2Pc in chloro-
form, DMF, and DMSO at room temperature are given in Figure
1. The split Q-band, which is characteristic of a metal-free phthalo-

N. Kabay, Y. Gök / Tetrahedron Letters 54 (2013) 4086–4090
4089
6. (a) Black, D. S. C.; McLean, L. A. J. Chem. Soc., Chem. Commun. 1968, 1004–1005;
(b) Westerby, B. C.; Juntunen, K. L.; Leggett, G. H.; Pett, V. B.; Koenigbauer, M. J.;
Purgett, M. D.; Taschner, M. J.; Ochrymowycz, L. A.; Rorabacher, D. B. Inorg.
Chem. 1991, 30, 2109–2120; (c) Krylova, K.; Kulatilleke, C. P.; Heeg, M. J.; Salhi,
C. A.; Ochrymowycz, L. A.; Rorabacher, D. B. Inorg. Chem. 1999, 38, 4322–4328;
(d) Siegfried, L.; Kaden, T. A. Helv. Chim. Acta 1984, 67, 29–38; (e) Groth, A. M.;
Lindoy, L. F.; Meenhan, G. V. J. Chem. Soc., Perkin Trans. 1 1996, 1553–1558; (f)
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(g) Chak, B. C. M.; McAuley, A. Can. J. Chem. 2006, 84, 187–195; (h) Gök, Y.;
Karaböcek, S. Z. Anorg. Allg. Chem. 1995, 621, 654–658; (i) Kabay, N.; Gök, Y.
Inorg. Chem. Commun. 2011, 14, 1880–1883; (j) Glenny, M. W.; van de Water, L.
G. A.; Vere, J. M.; Blake, A. J.; Wilson, C.; Driessen, W. L.; Reedijk, J.; Schröder, M.
Polyhedron 2006, 25, 599–612.
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
DMSO
DMF
Chloroform
7. (a) Ishikawa, J.; Sakamoto, H.; Nakamura, M.; Doi, K.; Wada, H. J. Chem. Soc.,
Dalton Trans. 1999, 191–200; (b) Sakamoto, H.; Ishikawa, J.; Otomo, M. Bull.
Chem. Soc. Jpn. 1995, 68, 2831–2836; (c) Glenny, M. W.; van de Water, L. G. A.;
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2004, 1953–1959; (d) Krylova, K.; Kulatilleke, C. P.; Heeg, M. J.; Salhi, C. A.;
Ochrymowycz, L. A.; Rorabacher, D. B. Inorg. Chem. 1999, 38, 4322–4328.
8. (a) Chak, B.; McAuley, A.; Whitcombe, T. W. Inorg. Chim. Acta 1996, 246, 349–
360; (b) Marques, F.; Guerra, K. P.; Gano, L.; Costa, J.; Campello, M. P.; Lima, L.
M. P.; Delgado, R.; Drew, M. G. B.; Felix, V. Dalton Trans. 1999, 4331–4339.
9. Compound 3: brown oil. IR (NaCl disc, cmꢀ1): 3391, 3013, 2935–2856, 1654: 1
H
NMR (300 MHz, CDCl3): d 8.41 (d, J = 4.8, 1H, PyH), 7.58 (t, J = 8.6, 1H, PyH), 7.21
(t, J = 8.0, 1H, PyH), 7.08 (d, J = 2.4, 1H, PyH), 4.82 (br, 2H, OH), 3.90–3.47 (m,
6H, PyCH2, OCH2), 2.50 (t, J = 12.8, 4H, NCH2), 1.60 (t, J = 11.6, 4H, CH2): 13C
NMR (75 MHz, CDCl3): d 159.72, 149.89, 137.72, 124.00, 123.06, 62.19, 60.05,
52.87, 29.20: Anal. Calcd. for C12H20N2O2: C, 64.28; H, 8.93; N, 12.51. Found: C,
64.37; H, 9.26; N, 12.32. MS (EI) m/z: 225 [M+1]+.
10. Compound 4: pale yellow oil. IR (NaCl disc, cmꢀ1): 3059, 2930–2864, 2544,
1668: 1H NMR (300 MHz, CDCl3): d 8.60 (d, J = 3.6, 1H, PyH), 8.00 (s, 1H, PyH),
7.80 (d, J = 1.2, 1H, PyH), 7.17 (t, J = 7.8, 1H, PyH), 3.95 (s, 2H, PyCH2), 3.25 (t,
J = 14.8, 2H, SH), 2.85 (m, 4H, NCH2), 2.60 (m, 4H, SCH2), 2.22 (m, 4H, CH2): 13
C
NMR (75 MHz, CDCl3): d 162.16, 149.33, 137.30, 125.77, 124.02, 51.42, 36.82,
30.98, 21.38: Anal. Calcd. for C12H20N2S2: C, 56.25; H, 7.81; N, 10.93. Found: C,
55.96; H, 7.60; N, 11.23. MS (EI): m/z 257 [M+1]+.
11. Kabay, N.; Gök, Y. Supramol. Chem. 2011, 23, 641–644.
12. Compound 6: pale orange oil. IR (NaCl disc, cmꢀ1): 3061, 3023, 2925–2868,
1596, 1338: 1H NMR (200 MHz, CDCl3): d 8.50 (d, J = 6.3, 1H, PyH), 8.01 (s, 1H,
PyH), 7.65 (d, J = 8.2, 2H, ArH), 7.42 (t, J = 7.6, 1H, PyH), 7.30 (d, J = 8.2, 2H, ArH),
7.10 (d, J = 6.5, 1H, PyH), 4.18 (s, 2H, PyCH2), 3.70 (m, 4H, NCH2), 3.20 (m, 4H,
NCH2), 2.85 (m, 8H, SCH2), 2.50 (s, 3H, CH3), 2.10 (m, 8H, CH2). 13C NMR
(50 MHz, CDCl3): d 160.23, 150.36, 145.39, 137.03, 130.10, 128.08, 124.26,
122.45, 62.51, 53.36, 48.30, 42.21, 35.56, 22.16: Anal. Calcd. for C25H37N3S3O2:
C, 59.17; H, 7.29; N, 8.28. Found: C, 59.43; H, 7.01; N, 8.05. MS (EI) m/z: 508
[M]+.
300
400
500
600
700
800
Wavelength (nm)
Figure 1. UV/vis spectra (1 ꢁ 10ꢀ5 M in CHCl3, DMF, and DMSO) of H2Pc.
13. Compound 7: yellow oil. IR (NaCl disc, cmꢀ1): 3296, 3061, 3013, 2925–2853,
1640: 1H NMR (200 MHz, CDCl3): d 8.54 (s, 1H, PyH), 8.04 (d, J = 8.2, 1H, PyH),
7.52 (d, J = 7.9, 1H, PyH), 7.14 (m, 1H, PyH), 4.14 (s, 2H, PyCH2), 3.71 (m, 4H,
NCH2), 3.58 (m, 4H, NCH2), 2.75 (m, 8H, SCH2), 2.10 (m, 8H, CH2), 1.58 (s, 1H,
NH). 13C NMR (50 MHz, CDCl3) d: 159.21, 148.74, 138.35, 127.48, 124.50, 59.25,
54.11, 43.52, 34.04, 30.91, 28.68. Anal. Calcd. for C18H31N3S2: C, 61.18; H, 8.78;
N, 11.89. Found: C, 60.93; H, 8.63; N, 11.76. MS (EI) m/z = 354 [M+1]+.
14. Gürek, A.; Bekarog˘lu, Ö. J. Porphyrins Phthalocyanines 1997, 1, 1077–1080.
15. Compound 9: waxy solid. IR (NaCl disc, cmꢀ1): 3073, 3058, 2925–2854, 2229,
1659: 1H NMR (200 MHz, CDCl3): d 8.51 (m, 2H, PyH), 8.01 (m, 2H, PyH), 7.53
(s, 2H, ArH), 7.48 (m, 2H, PyH), 7.21 (m, 2H, PyH), 4.19 (m, 4H, PyCH2), 3.78 (m,
Acknowledgment
This study was supported by the Research Fund of Pamukkale
University, Project number: 2008 FBE 002 (Denizli/Turkey).
References and notes
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1,
10H, NCH2), 3.61 (m, 10H, NCH2), 2.77 (m, 20H, SCH2), 1.99 (m, 16H, CH2). 13
NMR (50 MHz, CDCl3): 161.17, 148.13, 136.36, 130.02, 128.23, 127.48,
124.50, 115.41, 112.64, 58.31, 53.29, 42.95, 34.04, 29.64, 28.41. Anal. Calcd. for
C
d
2. (a) de la Torre, G.; Vazquez, P.; Agullo-Lopez, F.; Torres, T. J. Mater. Chem. 1998,
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C
48H70N8S6: C, 60.63; H, 7.36; N, 11.78. Found: C, 60.91; H, 7.59, N, 11.53. MS
(ESI) m/z = 951.41 [M+1]+.
16. Compound H2Pc: solid, mp >300 °C. IR (KBr disc, cmꢀ1): 3290, 3084, 3051,
2924–2856, 1641. 1H NMR (200 MHz, CDCl3): d 8.46 (m, 8H, PyH), 7.97 (m, 8H,
PyH), 7.68 (s, 8H, ArH), 7.45 (m, 8H, PyH), 7.26 (m, 8H, PyH), 4.25 (m, 16H,
PyCH2), 3.75 (m, 40H, NCH2), 3.58 (m, 40H, NCH2), 2.65 (m, 80H, SCH2), 2.01
(m, 64H, CH2). 13C NMR (50 MHz, CDCl3) d: 160.76, 155.27, 147.91, 136.79,
129.63, 128.01, 127.12, 124.97, 116.85, 58.82, 53.78, 43.25, 34.41, 29.11, 28.93.
Anal. Calcd. for C192H282N32S24: C, 60.59; H, 7.41; N, 11.78. Found: C, 60.35; H,
7.68; N, 11.51. UV/vis [CHCl3, kmax/nm (loge)]: 727 (4.14), 703 (4.23), 670
(4.00), 347 (5.23).
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