The first synthesis and characterization of new metal-free and metallophthalocyanine containing 33-membered crown ether moieties

Article abstract of DOI:10.1142/S1088424613500594

The synthesis and characterization of novel metal-free and metallophthalocyanines, fused symmetrically in non-peripheral positions with four octaoxamacrocycle has been synthesized by cyclotetramerization of the 2,5,8,11,14,20,23,26,29,32-decaoxatricyclo [

Full text of DOI:10.1142/S1088424613500594

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2013; 17: 1–7
DOI: 10.1142/S1088424613500594
Published at http://www.worldscinet.com/jpp/
The first synthesis and characterization of new metal-free
and metallophthalocyanine containing 33-membered
crown ether moieties
Fatma Akkus¸a, Nilgün Kabayb and Yas¸ar Gök*b
a Department of Chemistry, Mehmet Akif Ersoy University, Burdur, Turkey
b Department of Chemistry, Pamukkale University, Kınıklı/Denizli, Turkey
Dedicated to Professor Özer Bekaroğlu on the occasion of his 80th birthday
Received 10 January 2013
Accepted 4 April 2013
ABSTRACT: The synthesis and characterization of novel metal-free and metallophthalocyanines,
fused symmetrically in non-peripheral positions with four octaoxamacrocycle has been synthesized
by cyclotetramerization of the 2,5,8,11,14,20,23,26,29,32-decaoxatricyclo [31.2.2.115,19]octatriconta-
1(36),15,17,19(38),33(37),34-hexaene-34,35-dicarbonitrile (5) which was prepared by the reaction
of 3,6-bis[2-(2-{2-[2-(toluene-4-sulphonyl)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-phthalonitrile (3) and
1
1,3-dihydroxybenzene (4). The novel compounds were characterized by using elemental analysis, H,
13C NMR, IR, UV-vis and MS spectral data.
KEYWORDS: metallophthalocyanine, metal-free phthalocyanine, macrocyclic polyether, non-
peripheral, high dilution, template effect.
peripherally substituted phthalocyanines with macrocycle
INTRODUCTION
moieties have been well studied, but the non-peripheral
Phthalocyanines and metallophthalocyanines have
ones have received considerably less attention since their
attracted considerable attention owing to their variety,
first synthesis almost twenty-seven years ago [4].
optical, electronic, structural and coordination properties.
Since crown ethers were first recognized by Pedersen
They exhibit a number of extraordinary characteristics
as a relatively new class compounds, they have received
leading to potential applications in various scientific,
tremendous interest, especially in the fields of host-guest
technological and medical areas such as pigments,
chemistry [5], ion binding with metal and organic cations
catalysts, non-linear optical devices, liquid crystals,
and applications in the preparation of chemosensors,
Langmuir–Blodgett films, electrochromic devices, gas
molecular machines and supramolecular polymers
sensorsandphotosensitizersforphotodynamictherapy[1].
[6]. Self-assembly is a powerful tool for the creation
Metal cations over 70 different elements have been used
of extremely large and functioning supramolecular
as central atoms in the phthalocyanine cavity: therefore,
systems [7]. Rotaxanes are very convenient structures for
a large number of different metallophthalocyanines
ordering self-assembly processes. This kind of molecular
could be synthesized [2]. Coordination chemistry of
assemblies have potential applications in the areas of
phthalocyanines has encouraged researchers to specific
nanoscience switches and shuttles [8]. The most of the
products with certain properties required for applications
rotaxanes involving huge crown ether moieties such as
such as photocatalysts or electrocatalysts in the reduction
dibenzo-24-crown-8 or dibenzo-34-crown-10 have been
of carbon dioxide and oxygen [3]. The synthesis of the
templated by the hydrogen bonding between seconder
dialkylammonium ions and cyclic studied over the past
28 years in this area. Unfortunately, only a limited study
achieved to synthesize extremely huge crown ether
*Correspondence to: Yaşar Gök, email: gyasar@pau.edu.tr,
tel: +90 0258-296-3567, fax: +90 0258-296-3535
Copyright © 2013 World Scientific Publishing Company

2
F. AKKUS¸ ET AL.
units linked non-peripheral positions so far. Moreover,
there are a few examples of crown ethers containing
macrocycles more than 30-membered rings attached to
phthalocyanine structure [10].
In contrast with the phthalocyanines containing peri-
pherally macrocyclic donor sets, there are relatively fewer
studies on phthalocyanines involving non-peripheral
macrocyclic donor sets. In this paper, we report the
synthesis of the novel metal-free and metallophthalo-
cyanines which contain non-peripherally substituted four
33 membered macrocyclic polyethers.
mixture of toluene (120 mL) and the aqueous solution of
NaOH (10%, 150 mL). The organic phase was washed
with water (4 × 50 mL) and dried over CaCl2. The mixture
was filtered off, washed with toluene and evaporated
to dryness under reduced pressure. The yellow oily
product was purified by column chromatography [silica
gel (chloroform:ethyl acetate) (95:5)], to yield (3.78 g,
46%) of pale yellow waxy product (3). Anal. calcd. for
C38H48N2S2O14: C, 55.60; H, 5.85; N, 3.41%. Found C,
55.77; H, 5.53; N, 3.29. IR: n, cm-1 3040 (Ar-H), 3025
(Ar-H), 2881–2784 (C–H), 2232 (C≡N), 1597 (tosyl),
1486, 1353, 1286, 1189, 1137–1105, 1018, 925. 1H NMR
(300 MHz; CDCl3): dH, ppm 7.79–7.71 (4H, m, ArH),
7.43–7.34 (4H, m, ArH), 6.72 (2H, s, ArH) 4.18–4.3 (4H,
m, –OCH2), 3.84–3.74 (4H, m, –OCH2), 3.65–3.42 (24H,
m, –OCH2) 2.46 (6H, s, –CH3). 13C NMR (75 MHz;
CDCl3): dC, ppm 155.00, 144.61, 132.48, 129.64, 127.62,
122.13, 112.95, 104.46, 70.66, 70.31, 70.15, 69.70,
69.12, 68.78, 68.24, 21.36. MS (ES): m/z 821 [M + 1]+.
2,5,8,11,14,20,23,26,29,32-Decaoxa-tricyclo-
[31. 2. 2. 115, 19]octatriconta-1(36), 15, 17, 19-
(38),33(37),34-hexaene-34,35-dicarbonitrile (5). 1,3-
dihydroxybenzene (0.77 g, 7 mmol) was added directly to
a suspension of Cs2CO3 (10.50 g, 46.90 mmol), CsOTos
(3.0 g, 13.4 mmol) and tetrabutylammonium iodide
(TBAI) (0.7 g, 1.925 mmol) in dry DMF (450 mL) at 80 °C
under argon atmosphere and the mixture was stirred at this
temperature for 1 h. A mixture of the degassed solution
of 3 (5.74 g, 7 mmol) and CsOTos (5.39 g, 24.15 mmol)
in dry DMF (100 mL) was added dropwise to the above
mixture for 90 min. The reaction mixture was heated and
stirred at 100 °C for 7 days and monitored by a thin layer
chromatography [silica gel (hexane:acetone) (60:40)]. At
the end of this period, the mixture was cooled to room
temperature and filtered off, washed with dry chloroform.
The combined organic phases were evaporated to dryness
under reduced pressure. The crude product was dissolved
with dichloromethane (150 mL) and washed with water
(2 × 75 mL) and dried over MgSO4. The mixture was
filtered off, washed with dry dichloromethane and
evaporated to dryness under reduced pressure. The crude
product was purified by column chromatography [silica
gel (hexane:acetone) (60:40)], to yield (0.77 g, 22%) as
a pale yellow clear oil. Anal. calcd. for C30H38N2O10: C,
61.43; H, 6.48; N, 4.77%. Found C, 61.25, H, 6.74, N,
4.53. IR: n, cm-1 3080 (Ar–H), 3037 (Ar–H), 2945–2874
(C–H), 2230 (C≡N), 1585, 1482, 1448, 1351, 1281, 1184,
EXPERIMENTAL
General methods and materials
Unless otherwise stated, all preparations were carried
out in argon atmosphere in a vacuum line using standard
Schlenk techniques. Tetraethylenglycolditosylate (2)
[11] was prepared according to the method described
in the literature. 2,3-Dicyanohydroquinone and other
chemicals were purchased from Aldrich and used
without purification. All solvents were freshly purified
by standard procedures before use [12] and stored over
molecular sieves (4 Å). The purity of the novel products
was tested in each step by thin layer chromatography
1
(TLC Silica gel 60 F254 plate). H and 13C NMR spectra
were measured on Varian Mercury 200-NMR and
Varian Mercury Plus 300-MHz spectrometers in CDCl3
solutions, with Me4Si as the internal standard. Infrared
spectra were recorded on a Perkin Elmer Spectrum
FT-IR spectrometer. Mass spectra were measured on
micrOTOF and Micromass Quattro Ultima LC-MS/
MS instruments. Electronic spectra were recorded on a
Shimadzu UV-1601 spectrophotometer which is double-
beamed with thermostatically controlled cell block. The
elemental analysis was performed on a Costech ECS
4010 instrument. Melting points were determined in
open glass capillaries using a Buchi apparatus and are
uncorrected.
Synthesis
3,6-bis[2-(2-{2-[2-(toluene-4-sulphonyl)-ethoxy]-
ethoxy}-ethoxy)ethoxy]phthalonitrile (3).A solution of
tetraethyleneglycolditosylate (30.5 g, 60.75 mmol) in dry
acetonitrile (70 mL) was added dropwise to a suspension
of 2,3-dicyanohydroquinone (1.6 g, 10 mmol) in dry
acetonitrile (200 mL) under argon atmosphere at 60 °C
for 45 min. The reaction mixture was heated and stirred
at reflux temperature for 10 days and monitored by a thin
layer chromatography [silica gel (chloroform:ethanol)
(95:5)]. At the end of this period, the mixture was cooled
to room temperature and filtered off, washed with dry
ethyl acetate and then evaporated to dryness under reduce
pressure. The waxy crude product was extracted with the
1
1126–1065, 983. H NMR (300 MHz; CDCl3): dH, ppm
7.18 (2H, s, ArH), 7.04 (1H, t, ArH), 6.48 (3H, m, ArH),
4.15–3.96 (4H, m, OCH2), 3.80–3.71 (4H, m, OCH2),
3.65–3.46 (20H, m, OCH2), 3.36–3.28 (4H, m, OCH2).
13C NMR (75 MHz, CDCl3): dC, ppm 159.11, 154.65,
128.47, 116.05, 112.90, 107.56, 103.00, 71.46, 70.77,
69.11, 68.25, 67.13. MS (ES): m/z 587 [M + 1]+, 604
[M + H2O]+.
Metal-free phthalocyanine (H2Pc). A standard
Schlenk tube was charged with a solution of 4 (0.293 g,
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 2–7

THE FIRST SYNTHESIS AND CHARACTERIZATION OF NEW METAL-FREE AND METALLOPHTHALOCYANINE
3
0.5 mmol) in dry n-pentanol (2.5 mL) and five drops of
1,8-di-azabicyclo[5.4.0]undec-7-ene (DBU) under argon
atmosphere and degassed several times. The temperature
was gradually increased up to 155 °C and refluxed at
this temperature for 8 h. During this time, the mixture
became dark green. After cooling to room temperature,
dry methanol was added and stirred for 3 h to precipitate
completely. The mixture was filtered off, washed with
dry methanol and diethyl ether and then dried in vacuo.
The dark green product was purified by column
chromatography[silicagel(chloroform:methanol)(98:2)]
as eluent and gave green solid product. Yield 0.089 g
(15%), mp > 300 °C. Anal. calcd. for C120H154N8O40:
C, 61.38; H, 6.56; N, 4.77%. Found C, 61.19; H, 6.79;
N, 4.95. IR: n, cm-1 3320 (N–H), 3085 (Ar–H), 3052
(Ar–H), 2928–2864 (C–H), 1641 (C=N)meso, 1601, 148.8,
1353, 1262, 1186, 1114–1092, 976. 1H NMR (300 MHz;
CDCl3): dH, ppm 7.32 (12H, s, Ar–H), 7.17 (8H, m,
Ar–H), 6.48 (4H, t, Ar–H), 4.48–4.31 (64H, m, –CH2-),
3.88–3.71 (32H, m, –CH2-), 3.45–3.36 (32H, m, –CH2-),
-1.97 (2H, s, NH). 13C NMR (75 MHz; CDCl3): dC, ppm
158.78, 154.47, 155.17, 129.11, 112.51, 107.05, 103.29,
argon atmosphere, and reaction mixture was evacuated
several times and refilled with argon. Under this reaction
condition, the reaction mixture was heated and stirred at
155 °C for 8 h. The reaction mixture was then cooled to
room temperature, filtered and the residue was washed
with water, methanol and diethyl ether. The purification of
crude product was performed by column chromatography
[silica gel (chloroform:methanol) (98:2)] affording
desired product in 13.6% yield (0.082 g) as a dark green
solid. mp > 300 °C. Anal. calcd. for C120H152N8O40Co: C,
59.92; H, 6.32; N, 4.66; Co, 2.45%. Found C, 60.14; H,
6.07; N, 4.89; Co, 2.20. IR: n, cm-1 3076 (Ar–H), 3043
(Ar–H), 2956–2863 (C–H), 1624 (C=N)meso, 1599, 1491,
1350, 1258, 1211, 1092–1052, 971. UV-vis (CHCl3):
l
max, nm (log e) 726 (4.94), 653 (4.37), 320 (4.67). MS
(ES): m/z 2421.29 [M + H2O + 1]+.
RESULTS AND DISCUSSION
In this study, we give a full account of the synthesis
and characterization of novel metal-free (H2Pc) and cobalt
(CoPc) phthalocyanines by the cyclotetramerization
reaction of the dicyano compound containing p-phenylene-
m-phenylene-33-crown-10 moieties. Synthesis of 3,6-bis-
[2-(2-{2-[2-(toluene-4-sulphonyl)-ethoxy]-ethoxy}-
ethoxy)-ethoxy]-phthalonitrile(3)wasperformedasshown
in Scheme 1. The purification of 3 required column chrom-
atography on silica gel using chloroform:ethyl acetate
72.18, 71.89, 71.06, 69.83, 68.55. UV-vis (CHCl3): lmax
,
nm (log e) 800 (3.81), 732 (3.93), 354 (4.34). MS (ES):
m/z 2386.08 [M + K + 1]+.
Cobalt(II) phthalocyanine (CoPc). Dicyano
derivative 5 (0.293 g, 0.5 mmol) in dry N,N-dimethyle-
thanolamine (2 mL) and anhydrous CoCl2 (0.065 g,
0.5 mmol) was placed into a Standard Schlenk tube under
OH
O
O
O
O
O
OTos
OTos
HO
HO
CN
CN
i
NC
NC
O
TosO
O
O
2
OTos
+
+
O
O
O
OH
2
3
4
1
O
ii
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
N
O
O
O
O
O
O
O
N
N
N
N
iii
NC
NC
N
M
N
O
O
O
O
O
O
N
O
O
O
5
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
M: 2H, Co
Scheme 1. (i) K2CO3, dry CH3CN, Ar, 60 °C, 10 days; (ii) Cs2CO3, CsOTos, TBAI, dry DMF, Ar, 80 °C, 7 days; (iii) dry n-pentanol,
DBU, reflux, 8 h. (H2Pc); anhyd. CoCl2, dry N,N-dimethylethanolamine, reflux, 8 h (CoPc)
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 3–7

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F. AKKUS¸ ET AL.
1
(95:5) as an eluent and gave 46% yield. In the H NMR
spectrum of 3, the presence of significant resonances for
tosyl and hydroquinone groups as dublets and multiplets
at d = 7.79–7.71 and 7.43–7.34 ppm, respectively, is one
of the verification of condensation reaction (Scheme 1).
This spectrum displayed relatively well-defined resonance
signals in the polyetheric moieties corresponding as
expected to the typical signals of the precursor compound
(2). The 13C NMR spectrum of the same compound clearly
indicated the presence of cyano (d = 112.95 ppm), tosyl
(d = 144.61, 132.48, 129.64, 127.62 ppm) and aliphatic
carbons at d = 70.66, 70.31, 70.15, 69.70, 69.12, 68.78,
68.24, 21.36 ppm, respectively. The IR spectrum of
compound 3 also exhibited characteristic vibrations
related C≡N and tosyl groups at 2232 and 1598 cm-1. The
ES mass spectrum at m/z = 821 [M + 1]+ and elemental
analysis of this compound supported the condensation
reaction between the starting materials (1 and 2).
the macrocyclization reaction. On the other hand, the
presence of new resonances for 1,3-dihydroxybenzene
moiety as triplet and multiplet at d = 7.04 and 6.48
ppm, respectively, is one of the verifications of
macrocyclization reaction. Observed characteristic
signals of proton-decoupled 13C NMR spectrum of
the compound for the novel aromatic carbon atoms
at d = 159.11, 128.47, 107.56 and 103.00 ppm clearly
suggested the macrocyclization reaction has occurred.
The results of NMR spectra are shown in Figs S1 and S2
(Supporting information). In the IR spectrum of 5, very
specific stretching vibrations of tosyl groups at 1598 cm-1
disappeared after the macrocyclization formation. The
mass spectrum of 5 contained an intense peak at m/z =
587 [M + 1]+ for the parent ion, which can be attributed
to the formation of dicyano derivative (5).
Condensation of four molecules of dicyano compound
(5) containing 33-membered macrocyclic polyether
moiety into the metal-free phthalocyanine were carried
out in dry n-pentanol and a catalytic amount of DBU
as the ring-forming catalyst [13]. After purification by
column chromatography, the desired compound H2Pc
was obtained in 15% yield. The 1H NMR spectrum of this
compound in CDCl3 exhibits the characteristic signals of
macropolycycle and phthalocyanine moieties. The strong
shelding of the inner core protons of this compound was
manifested by a broad resonance at d = -1.97 ppm [14] at
high concentration which could be attributed to the NH
resonance and identified easily with deuterium exchange.
The synthesis of the cyano compound 5 (Scheme 1)
containing 33-membered decaoxa macrocycle was
performed by condensation reaction between compound
3 and 1,3-dihydroxy benzene (4). Treatment of 3 with
4 in dry DMF in the presence of Cs2CO3, CsOTos
and TBAI via high dilution technique resulted in the
formation of desired decaoxa macrocycle 5 in 22% yield
as pale yellow oily product after purification by column
chromatography [silica gel (hexane:acetone)(60:40)]. In
1
the H NMR spectrum of 5, the chemical shifts of tosyl
protons in the precursor compound (3) disappeared after
Fig. 1. Mass spectrum of H2Pc
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 4–7

THE FIRST SYNTHESIS AND CHARACTERIZATION OF NEW METAL-FREE AND METALLOPHTHALOCYANINE
5
In 13C NMR spectrum of this compound, all resonances
are identical for the precursor non-peripherally substituted
dicyanoderivativeexceptfortheC≡Ncarbonsasexpected.
The chemical shift appeared at d = 155.17 ppm of this
compound should be related to inner core C=N signals
[15]. Cyclotetramerization of the dicyano derivative was
confirmed by the disappearance of the significant C≡N
vibrations at 2230 cm-1 in the IR spectrum of H2Pc. The
difference between the IR spectra of 5 and H2Pc are clear
from the presence of some characteristic vibrations such
as N–H and C=N at 3320 and 1641 cm-1, respectively. The
structure of metal-free phthalocyanine were confirmed by
elemental analysis, as well as mass spectral (ES-MS) data
at 2386.08 [M + K + 1]+ (Fig. 1).
Cyclotetramerization of macrocyclic polyether
substituted dicyano compound (5) to give the cobalt(II)
phthalocyanine (CoPc) was carried out in dry N,N-
dimethylethanolamine in the presence of anhydrous
CoCl2 [13, 16]at155°Cfor8haffordedthecorresponding
tetra-substituted metallophthalocyanine (CoPc) in 13.6%
yield as dark green solid after purification by column
chromatography. Cyclotetramerization of the dicyano
compound (5) was confirmed by the disappearance of
the sharp C≡N stretching vibration at 2230 cm-1 of the
precursor dicyano derivative (5) and the presence of C=N
resonance at 1624 cm-1 also confirmed the formation of
Fig. 2. Electronic absorbtion spectra of H2Pc (―) and CoPc
(―) in chloroform (concentration = 1.10-5 M)
cobalt(II) phthalocyanine. The rest of the IR spectrum
of CoPc closely resemble that of 5, including the
characteristic vibrations of the aromatic and polycyclic
typical decreasing of intensity and widening of Q-band
etheric groups. The mass spectrum of CoPc, which
absorptions. The lower energy bands at lmax = 726 and
showedtheexpectedpeakatm/z=2421.29[M+H2O+1]+,
653 nm belonging to the cobalt(II) phthalocyanine are
due to the monomeric species at the non-peripheral
also confirmed the proposed structure.
The synthesized metal-free phthalocyanine displayed
positions, which have increased values at the longest
noticeable electronic spectrum in chloroform (Fig. 2)
wavelength Q-band absorption compared to its analogs
with two significant absorption bands, one of them in the
and demonstrate less aggregation, prevent macrocycles
visible region at about 800–732 nm corresponding to the
from getting too close to each other [25]. The typical
split Q-band due to its D2h symmetry, as Qx and Qy bands
monomeric behavior evidenced by a single absorptions
[17], attributed to the p→p* transition from HOMO to the
species with D4h symmetry [26]. The disaggregation of
LUMO orbitals. The other band is B band in the UV part
cobalt(II) phthalocyanine can be referred to the presence
of the spectrum at about 354 nm, arising from the deeper
of central metal ion.
p→p* transition [18]. The Q-band of the non-peripherally
crown ether substituted metal-free phthalocyanine is red-
shifted-significantly compared to peripherally substituted
analogs [19]. Bathochromic shift of Q-band is also known
CONCLUSION
in symmetric phtalocyanines bearing non-peripheral
chalcogenic donors such as sulphur, selenium [20] and,
rarely oxygen [21]. However, in this study we observed
bahtochoromic shift in the synthesized 33-membered
symmetrical phtalocyanine bearing macrocyclic oxygen
donors [22]. This situation has been explained to be due
to LCAO coefficient as its being greater than those at the
peripheral positions [23]. The shape of this absorption
spectrum is also similar to that of core-modified
phthalocyanine analogs with a seven membered ring
moiety [24]. In contrast to the cobalt(II) phthalocyanine,
as it is shown in Fig. 2, the metal-free phthalocyanine is
strongly aggregated in chloroform solution due to the
In this study, novel metal-free and phthalocyaninato
cobalt(II) complex containing symmetrically four
33-membered crown ether units were synthesized
by cyclotetramerization reaction of 2,5,8,11,14,20,23,-
26,29,32-decaoxatricycle[31.2.2.115,19]octatriconta-
1(36),15,17,19(38),33(37),34-hexaene-34,35-
dicarbonitrile (5) in the presence of a strong organic
base and anhydrous CoCl2. The new compounds were
characterized by standard methods including elemental
analysis, 1H NMR, 13C NMR, IR, UV-vis and MS
techniques. The ground state electronic absorption spectra
of the phthalocyanines were also described in chloroform.
Metal-free phthalocyanine (H2Pc) showed noticeable
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 5–7

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F. AKKUS¸ ET AL.
Q-band absorption at 800 nm compared to the peripherally
substituted phthalocyanines analog in chloroform. The
noticeable red-shifted band at 800 nm for H2Pc and 726
nm for CoPc are due to monomeric and non-aggregated
species. This absorption band can be shifted to the QD
(singlet oxygen quantum yield) values for photodynamic
therapy (PDT) applications. This significant red-shift
band is also important and will receive further attention
for various near-IR investigations. The intensity of this
absorption in H2Pc has also decreased as expected.
4. a) Koray AR, Ahsen V and Bekaroğlu Ö. J. Chem.
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Supporting information
1H and 13C NMR spectra of 5 in CDCl3 are given in
the supplementary material (Figs S1–S2). This material
is available free of charge via the Internet at http://www.
worldscinet.com/jpp/jpp.shtml.
8. Ashton PR, Chrystal EJT, Glink PT, Menzer S, et al.
Chem. Eur. J. 1996; 2: 709–728.
Acknowledgements
9. a) Martinez-Diaz MV, Rodriguez-Morgooe MS,
Feiters MC, van Kan PJM, Nolte RJM, Stoddart
JF and Torres T. Org. Lett. 2008; 2: 1057–1060. b)
Sickcken DE, van Tilborg MM, Roks MFM, Hen-
driks R, Drenth W and Nolte RJM. J. Am. Chem.
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V, Simon J, ibid. 1994; 116: 5352–5361.
This study was supported by the Research Fund of
Pamukkale University, Project number 2009 FBE 033
(Denizli/Turkey).
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