Synthesis, extraction and chromogenic properties of Amidoazocalix[4]arenes and their telomer derivatives

Article abstract of DOI:10.1080/10610278.2014.910603

The synthesis, extraction and chromogenic properties of calix[4]arenes, carrying phenylazo and amido groups on their upper and lower rims, respectively, are described. Novel azocalix[4]arene amides (1a-d, 2a-d, 3a-d) and some of their telomers (T1a-T1d) have been synthesised and characterised by spectroscopic methods as well as elemental analysis techniques. Compounds 1c and 2b were additionally characterised by two-dimensional nuclear magnetic resonance spectroscopic methods. Some of the compounds were examined by absorption spectra using different solvents. The colour changes of the resulting solutions can be observed by the naked eye. Metal extraction abilities of compounds have been investigated comparatively. Telomer structures of azocalix[n]arenes exhibited higher extraction rates compared to those of their monomers. Products obtained under this study, especially telomers, can be used in the field of ion-selective electrodes.

Full text of DOI:10.1080/10610278.2014.910603

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Synthesis, extraction and chromogenic properties of
Amidoazocalix[4]arenes and their telomer derivatives
a
a
Özlem Özen Karakuş & Hasalettin Deligöz
a
Department of Chemistry, Pamukkale University, 20017 Denizli, Turkey
Published online: 29 Apr 2014.
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To cite this article: Özlem Özen Karakuş & Hasalettin Deligöz (2015) Synthesis, extraction and chromogenic
properties of Amidoazocalix[4]arenes and their telomer derivatives, Supramolecular Chemistry, 27:1-2, 110-122, DOI:
10.1080/10610278.2014.910603
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Supramolecular Chemistry, 2015
Vol. 27, Nos. 1–2, 110–122, http://dx.doi.org/10.1080/10610278.2014.910603
Synthesis, extraction and chromogenic properties of Amidoazocalix[4]arenes and their
telomer derivatives
1
¨
Ozlem Ozen Karaku s¸ * and Hasalettin Delig o¨ z
¨
Department of Chemistry, Pamukkale University, 20017 Denizli, Turkey
(
Received 18 February 2014; accepted 28 March 2014)
The synthesis, extraction and chromogenic properties of calix[4]arenes, carrying phenylazo and amido groups on their upper
and lower rims, respectively, are described. Novel azocalix[4]arene amides (1a–d, 2a–d, 3a–d) and some of their telomers
(
T1a–T1d) have been synthesised and characterised by spectroscopic methods as well as elemental analysis techniques.
Compounds 1c and 2b were additionally characterised by two-dimensional nuclear magnetic resonance spectroscopic
methods. Some of the compounds were examined by absorption spectra using different solvents. The colour changes of the
resulting solutions can be observed by the ‘naked eye’. Metal extraction abilities of compounds have been investigated
comparatively. Telomer structures of azocalix[n ]arenes exhibited higher extraction rates compared to those of their
monomers. Products obtained under this study, especially telomers, can be used in the field of ion-selective electrodes.
Keywords: calixarene; amidoazocalix[4]arene; telomer; 2D NMR; metal extraction; absorption property
Introduction
and two or more aromatic rings. The colour properties of
organic dyes depend on their chromophore groups and
some of crystalline organic dyes also depend on the
crystallographic arrangement of molecules in the solid
state (5).
Calix[n ]arenes can be synthesised by base-catalysed
condensation of para-substituted phenols with formal-
dehyde. They are used in designing and synthesising
artificial receptors for the development of chromogenic
ionophores. They are also used in the molecular recognition
of ionic species of chemical and biological interest. Thus,
they are regarded as an important class of building blocks,
which is very well documented in supramolecular
chemistry (1). In detection of metals, polymerised
calixarenes, called telomers, can carry more metal ions
than the monomer form of calixarenes. The enhancement of
this binding property is mainly due to the nature of the
linkers. Selective signalling of heavy metal ions is very
important for detection and recognition of toxic metal ions
in various systems (2).
For the past decade, our research group has persistently
focused on mimicking the active site of mononuclear azo
compounds. In our studies, calix[4 and 6]arene macro-
cycles are used to isolate the metal centre to prevent
dimerisation and hence play the role of the host–guest
complexes. The hydrophobic cavity in the azocalixarene
structures provides secondary interaction between the
azocalixarene molecule itself and a probable guest ion or
molecule (6). More recently, the interest of our research
group moved into developing systems that can bind two
˚
metal centres at controlled distances higher than 4 A in
Azocalix[n]arenes are generated by the insertion of
nitrogen atoms into the p-positions of the calixarene
structures. They have several isomers based on the position
of the inserted nitrogen atoms and molecular ring size (3).
Azo compounds are one of the most widely used classes of
dyes. They are used in various fields such as the dyeing of
textile fibers, colouring of differing materials, biomedical
studies and advanced applications in organic synthesis (4).
Advanced applications of azo compounds in organic
synthesis include sensor molecules, metal electrodes and
indicators. Moreover, calixarenes gain chromogenic
activity with azo groups. These compounds are an
important class of organic colourants and consist of one
or more conjugated chromophore azo (ZNvNZ) group
order to escape the thermodynamic sink leading to the
formation of bridged and electronically coupled dinuclear
complexes (7). Indeed, many enzymes, consisting of two
metal ions displaying different functions (8), raise
interesting questions relative to selective binding of two
different metal ions at twodifferent sites. The reason for this
situation is mutual structural roles, selective metal ion
loading and trafficking and thus translocation processes (9).
So far, very few synthetic systems involving azocalix
(4(arenes have been studied (10). Chung and co-workers
have synthesised an azocalix(4(arene molecule with bis4-
0
(4 -methoxyphenylazo) phenol unit and a bisallyl group on
its upper rim (11). They observed a high extraction ability
of the synthesised compound for particular mercury ions
*Corresponding author. Email: oozen@pau.edu.tr
q 2014 Taylor & Francis

Supramolecular Chemistry
111
2
Hg ) among various metal ions. Lu et al. have
þ
(
MALDI-TOF and elemental analyses were performed
in the TUBITAK Laboratory (Center of Science and
Technology Research of Turkey).
synthesised a water-soluble azocalixarene derivative and
reported its application as highly selective chromogenic
ionophores in recognition of chromium(III) ions (12).
Reinhoult et al. have synthesised chromogenic azocalix[4]
arene containing nitrophenylazo and amide groups and
Preparation of the ligands
2
þ
reported its high extraction ability towards Pb among
various metal ions (13).
p-tert-Butylcalix(4(arene (16), calix(4(arene (17), 25,27-
di(ethoxycarbonylmethoxy)-26,28-hydroxycalix(4(arene,
calix[4]aren(amido)mono-crown derivatives (1–3) (10)
and their azo derivatives were prepared according to the
procedure below.
Among azophenolic supramolecules, azocalix[4]are-
nes are unique in their efficient ionophoric properties
2
þ
þ
towards some important guest ions such as Ca or K . Azo
groups, which are considered to be chromogenic centres,
cannot be referred to as metal-chelating sites. Various
efforts have been performed on lower rim modification
of azocalix[4]arenes in order to bring metal-binding
ability. But, azocalix[4]arenes without lower rim modifi-
cations can also bind transition metal ions effectively (14).
Nowadays, selective transportation of metal ions by
calixarenes plays a crucial role in ion recognition for
environment and biological systems. Rao and his
coworkers demonstrated selective recognition of Asp,
Glu and GSH by lower rim 1,3-diamido conjugates of
calix[4]arene possessing terminal ZCOOH moieties by
fluorescence spectroscopy (15).
General procedure for the synthesis of amidoazocalix[4]
arenes
The following procedure was used to transform amidoca-
lix[4]arenes (1,2,3) in to the corresponding azo series.
A solution of p-substituted phenyldiazonium chloride
was prepared from p-substituted aniline (1.84 mmol),
sodium nitrite (2.76 mmol) and conc. HCl (9.24 mmol) in
water (2 mL). The resulting solution was added slowly to a
solution of cold (58C) amidocalix[4]arene (0.5 g,
0.88 mmol) and sodium acetate trihydrate (9.36 mmol) in
DMF/MeOH (13 mL, 8:5, v/v). The resulting yellow
suspension was kept between 0 and 58C for 10 h. Then, the
suspension was brought to room temperature before
acidifying with aqueous HCl (60 mL, 4 N). The resulting
mixture was firstly warmed up to 608C and kept at that
temperature for 30 min to give an amidoazocalix[4]arene
residue. After filtering and washing with water, the solid
residue was purified by column chromatography with
hexane and ethyl acetate as an eluent.
In this study, synthesis and characterisation of novel
amidoazocalix[4]arene monomers (1a–d, 2a–d, 3a–d)
and telomers (T1a–T1d) containing different functional
groups (Scheme 1) have been presented. Absorption and
extraction properties of synthesised compounds have also
been demonstrated in this work.
Compound 1a: The solid was eluted with hexane/
ethyl acetate (3:1,v/v) and gave 0.45 g (60%) of a red
Experimental
General methods
1
powder, mp.: 3158C (dec): H NMR (CDCl ) d: 3.70 (d,
3
Solvents were purified and dried by standard methods
prior to use. All reactions were carried out under nitrogen.
Column chromatography purification of products was held
by using silica gel (0.040–0.063 nm). Reactions were
monitored by TLC on silica gel plates and visualised by
UV light.
J ¼ 13.42 Hz, 4H, ArCH Ar), 3.76 (s, 4H, amido-CH ),
2
2
4.21 (d, J ¼ 13.32 Hz, 4H, ArCH Ar), 4.62 (s, 4H,
2
O-CH ), 7.00 (t, 2H, ArH-calix), 7.20 (d, 4H, ArH-calix),
2
7.62 (d, 4H, ArHZNvN), 7.77 (d, 4H, ArHZNvN), 7.79
(s, 4H, ArH-calix), 8.40 (s, 2H, NH), 8.88 (s, 2H, ArOH).
1
3
C NMR (75 MHz CDCl ): 167.7, 151.9, 148.9, 133.0,
3
All the solvents used were dried and distilled by the
usual procedures before use. Melting points of the
products were measured with Electrothermal IA9100
digital melting point apparatus in capillaries sealed under
nitrogen and are uncorrected. UV–vis spectra were
obtained with Shimadzu 1601 UV-Visible recording
132.1, 129.3, 129.2, 127.4, 127.1, 125.0, 124.7, 123.1,
120.7, 74.7, 39.3, 31.4. Anal. calcd for C H N O : C,
4
6 38 8 10
64.03; H, 4.44; N, 12.99. Found: C, 64.28; H, 4.63; N,
12.77.
Compound 1b: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.42 g (%52) of an
1
orange powder, mp.: 2708C. H NMR (CDCl ) d: 3.69
˙
spectrophotometer (Tetra, Izmir, Turkey). IR spectra
3
were recorded by Mattson 1000 FT-IR spectrometer
13
(d, J ¼ 13.49 Hz, 4H, ArCH Ar), 3.74 (s, 4H, amido-
2
1
Tetra, Izmir, Turkey) with KBr pellets. The H and
˙
(
C
CH ), 4.22 (d, J ¼ 13.41 Hz, 4H, ArCH Ar), 4.63 (s, 4H,
2
2
NMR spectra were recorded with a Bruker FT-400 MHz
spectrometer (Bruker, Istanbul, Turkey) at room tempera-
ture (CDCl ). 2D NMR spectra were recorded with a
OZCH ), 6.95 (t, 2H, ArH-calix), 7.16 (d, 4H, ArH-
2
calix), 7.63 (d, 4H, ArHZNvN), 7.74 (d, 4H,
ArHZNvN), 7.78 (s, 4H, ArH-calix), 8.38 (s, 2H,
3
1
NH), 8.86 (s, 2H, ArOH). C NMR (75 MHz CDCl3):
3
Bruker DPX-300 MHz spectrometer (Bruker, Istanbul,
Turkey) at Ataturk University (Erzurum, Turkey).
167.2, 155.2, 151.5, 149.0, 146.4, 132.3, 132.3, 130.1,

¨
O.O. Karaku s¸ and H. Delig o¨ z
¨
1
12
O
AlCl3
O
OH OH
O
Br-CH -C-OC H
5
2
2
CH2
Toluene
CH2
OH OH OH HO
K CO \MeCN
2
3
C
O
C
O
OH OH OH HO
OC H
OC H
2
5
2
5
H N
2
Toluene-MeOH(1:1)
Toluene-MeOH(1:1)
N
NH2
Toluene-MeOH(1:1)
CH2
NH2
H2N
NH2
O
OH OH
O
O
OH OH
O
CH2
H C
O
OH OH
O
2
1
CH2
2
3
CH2
CH
O C
HN
C
O
CH
2
2
O
C
O
NH
C
HN
O
C O
C
NH
CH2
CH2
NH
HN
N
N
R
R
R
NaNO \HCl
2
NaNO \HCl
2
NaNO \HCl
NH2
2
NH2
NH2
R
R
R
R
R
R
R
R
R
1
1
1
1
a : –NO2
2a : –NO2
2b : –Br
3a : –NO2
b : –Br
b : –Br
3
N
N
N
N
N
N
N
N
N
c : –CH3
2c : –CH3
2d : –OCH3
3c : –CH3
N
N
N
d : –OCH3
3d : –OCH3
O
OH OH
O
O
OH
O
O
CH2
OH OH
O
OH
CH2
H C
CH2
CH2
2
HC2
C
O
O
C
C
O
C O
O C
HN
C
O
NH
NH
CH2
HN
HN
CH2
NH
N
N
TsO
Dioxane / NaH
O OTs
5
R
R
R
R
R
R
R
N
N
N
N
N
N
N
N
N
N
N
N
T1a : –NO2
T1b : –Br
O
O
O
O
T1c : –CH3
O
O
O
CH2
O
OH
O
CH2
OHO
O
O
O
H C
O
O
O
O
O
T1d : –OCH3
CH2
2
CH2
CH2
O C
HN
O C
HN
O C
NH
O C
NH
O C
HN
O C
NH
Scheme 1. Synthesis of amidoazocalix(4(arenes and telomers.
128.0, 127.2, 124.7, 124.4, 124.0, 74.9, 39.2, 31.4.Anal.
calcd for C H Br N O : C, 59.37; H, 4.12; N, 9.03.
7.19 (d, 4H, ArH-calix), 7.32 (d, 4H, ArHZNvN), 7.78
(s, 4H, ArH-calix), 7.80 (d, 4H, ArHZNvN), 8.45 (s, 2H,
4
6
38
2 6 6
1
3
Found: C, 59.68; H, 4.43; N, 9.28.
Compound 1c: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.40 g (%58) of a yellow
NH), 8.82 (s, 2H, ArOH). C NMR (75 MHz CDCl3):
167.3, 154.7, 150.8, 148.9, 146.6, 140.9, 132.4, 130.1,
129.7, 127.9, 127.2, 124.1, 122.5, 74.8, 39.3, 31.5, 21.5.
Anal. calcd for C H N O : C, 71.98; H, 5.54; N, 10.49.
1
powder, mp: . 3208C (dec): H NMR (CDCl ) d: 2.45
3
48 44 6 6
(
s, 3H, ArZCH ), 3.71 (d, J ¼ 13.48 Hz, 4H, ArCH Ar),
Found: C, 71.68; H, 5.88; N, 10.62.
Compound 1d: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.42 g (58%) of a dark
3
2
3
ArCH Ar), 4.66 (s, 4H, O-CH ), 6.96 (t, 2H, ArH-calix),
.76 (s, 4H, amido-CH ), 4.24 (d, J ¼ 13.38 Hz, 4H,
2
2
2

Supramolecular Chemistry
113
1
yellow powder, mp: 3128C (dec): H NMR (CDCl ) d: Ar), 3.58 (s, 4H, amido-CH ), 3.80 (s, 6H, OZCH ), 4.18
3
2
3
3
.73 (d, J ¼ 13 Hz, 4H, ArCH Ar), 3.77 (s, 4H, amido-
(d, J ¼ 13.47 Hz, 4H, ArCH Ar), 4.45 (s, 4H, O-CH ),
2
2
2
CH ), 3.92 (s, 6H, OCH ), 4.25 (d, J ¼ 13 Hz, 4H,
6.60 (t, 2H, ArH-calix), 6.78 (d, 4H, ArH-calix), 6.95 (d,
4H, ArHZNvNZ), 7.15 (s, 4H, ArH-calix), 7.55 (s, 1H,
NH), 7.65 (s, 1H, NH), 7.70 (s, 2H, ArOH), 7.65 (d, 4H,
2
3
ArCH Ar), 4.67 (s, 4H, O-CH ), 6.98 (t, 2H, ArH-calix),
2
2
7
.03 (d, 4H, ArHZNvN), 7.20 (d, 4H, ArH-calix), 7.76
s, 4H, ArH-calix), 7.90 (d, 4H, ArHZNvN), 8.47 (s, 2H,
1
3
(
NH), 8.80 (s, 2H, ArOH). C NMR (75 MHz CDCl3):
ArHZNvNZ). C NMR (75 MHz CDCl ): 168.1, 154,7
3
1
3
152.2, 150.4, 132.1, 129.6, 129.2, 128.2, 127.7, 126,5,
124.3, 120.6, 114.2, 75.0, 55.6, 37.7, 31.2, 25.1. Anal.
calcd for C H N O : C, 69.75; H, 5.62; N, 9.76. Found:
1
1
67.3, 161.6, 154.3, 148.9, 147.0, 146.6, 132.4, 130.0,
27.8, 127.2, 124.3, 123.9, 114.2, 74.7, 55.5, 39.3, 31.4.
5
0 48 6 8
Anal. calcd for C H N O : C, 69.22; H, 5.32; N, 10.09.
4
C, 69.92; H, 5.78; N, 9.83.
Compound 3a: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.51 g (70%) of an orange
8 44 6 8
Found: C, 68.99; H, 5.44; N, 10.20.
Compound 2a: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.48 g (64%) of a yellow
1
powder, mp: 2408C (dec): H NMR (CDCl ) d: 3.42 (dd,
3
o
powder, mp: 232 C (dec): H NMR (CDCl ) d: 1.81
1
J ¼ 13.19 Hz, 4H, ArCH Ar), 3,62 (s, 4H, ArCH Ar), 4.20
3
2
2
(
s, 4H, amido-CH ), 3.66 (d, J ¼ 13.68 Hz, 4H, ArCH -
(d, 2H, amido-CH ), 4.30 (d, 2H, Amido-CH ), 4.48
2 2
2
2
Ar), 3.68 (s, 4H, amido-CH ), 4.25 (d, J ¼ 13.56 Hz, 4H,
(s, 2H, OZCH ), 4.63 (s, 2H, OZCH ), 6.68 (t, 2H, ArH-
2 2
2
ArCH Ar), 4.59 (s, 4H, O-CH ), 6.86 (t, 2H, ArH-calix),
2
calix), 6.80 (t, 2H, ArH-pyridyl), 6.90 (d, 2H, ArH-
pyridyl), 7.10 (d, 4H, ArH-calix), 7.50 (d, 2H,
ArH-pyridyl), 7.65 (d, 2H, ArH-pyridyl), 7.80 (d, 4H,
ArHZNvNZ), 8.00 (s, 4H, ArH-calix), 8.38 (d, 4H,
ArHZNvNZ), 8.52 (s, 2H, ArOH), 9.11 (s, 1H, NH),
2
7
.02 (d, 4H, ArH), 7.50 (s, 2H, NH), 7.85 (s, 2H, ArOH),
.87 (s, 4H, ArH-calix), 8.01 (d, 4H, ArHZNvNZ), 8.38
7
1
3
(
d, 4H, ArHZNvN). C NMR (75 MHz CDCl ): 167.8,
3
1
1
52.2, 150.4, 148.3, 146.4, 132.2, 131.3, 129.6, 127.6,
26.6, 124.9, 123.1, 120.7, 75.1, 37.7, 31.2, 25.2. Anal.
1
3
9.20 (s, 1H, NH). C NMR (75 MHz CDCl ): 169.0,
3
calcd for C H N O : C, 64.71; H, 4.75; N, 12.58.
8 42 8 10
158.9, 152.7, 149.0, 146.0, 136.5, 132.9, 132.0, 130.0,
129.5, 128.8, 127.5, 126.3, 124.7, 123.0, 121.7, 120.6,
119.6, 71.8, 44.8, 31.5. Anal. calcd for C H N O : C,
4
Found: C, 64.98; H, 4.88; N, 12.73.
Compound 2b: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.48 g (60%) of an orange
5
6 46 10 10
66.00; H, 4.55; N, 13.75. Found: C, 66.29; H, 4.64; N,
13.89.
Compound 3b: The solid was eluted with hexane/
1
powder, mp: 2408C (dec): H NMR (CDCl ) d: 1,73 (s, 4H,
3
amido-CH ), 3.57 (s, 4H, amido-CH ), 3.61 (d,
2
2
J ¼ 13.59 Hz, 4H, ArCH Ar), 4.15 (d, J ¼ 13.56 Hz, 4H,
ethyl acetate (3:1, v/v) and gave 0.52 g (68%) of a brown
1
powder, mp: 1508C (dec): H NMR (CDCl ) d: 3.62 (d,
2
ArCH Ar), 4.50 (s, 4H, O-CH ), 6.76 (t, 2H, ArH-calix),
2
2
3
6
.93 (d, 4H, ArH-calix), 7.47 (s, 2H, NH), 7.57 (d, 4H,
ArHZNvNZ), 7.60 (s, 2H, ArOH), 7.70 (d, 4H,
J ¼ 13 Hz, 4H, ArCH Ar), 4.15 (d, J ¼ 13 Hz, 4H,
2
ArCH Ar), 4.55 (s, 4H, NHZCH ) 4.70 (s, 4H, O-CH )
2
2
2
1
3
ArHZNvNZ), 7.74 (d, 4H, ArH-calix). C NMR
75 MHz CDCl ): 167.7, 155.4, 151.5, 150.5, 146.2, 132.3,
6.76 (t, 2H, ArH-calix), 6.95 (d, 4H, ArH-calix), 6.80
(t, 2H, ArH-pyridyl), 7.32 (d, 2H, ArH-pyridyl), 7.58 (d,
2H, ArH-pyridyl), 7.65 (d, 4H, ArHZNvNZ), 7.75 (d,
4H, ArHZNvNZ), 7.70 (s, 4H, ArH-calix), 8.21(d, 2H,
ArH-pyridyl), 8.22 (s, 2H, ArOH), 8.85 (s, 1H, NH), 8.95
(
3
1
3
4
31.6, 130.0, 128.2, 126.7, 124.8, 124.2, 124.1, 75.1, 37.7,
1.2, 25.2.Anal. calcd for C H Br N O : C, 60.14; H,
4
8
42
2 6 6
.42; N, 8.77.Found: C, 60.39; H, 4.60; N, 8.48.
Compound 2c: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.47 g (67%) of a yellow
1
3
(s, 1H, NH). C NMR (75 MHz CDCl ): 167.9, 156.5,
3
155.6, 151.1, 149.3, 146.0, 136.7, 132.6, 132.3, 131.9,
130.0, 129.7, 128.9, 127.8, 127.1, 126.5, 124.0, 122.4,
74.7, 45.4, 31.6. Anal. calcd for C H Br N O : C, 61.89;
o
powder, mp: 294 C (dec): H NMR (CDCl ) d: 1,83
1
3
(
s, 4H, amido-CH ), 2.48 (s, 6H, ArZCH ), 3.66 (s, 4H,
2 3
56 46
2 8 6
amido-CH ), 3.69 (d, J ¼ 13.61 Hz, 4H, ArCH Ar), 4.25
H, 4.27; N, 10.31. Found: C, 62.50; H, 4.05; N, 10.48.
Compound 3c: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.50 g (73%) of a brown
2
2
(
d, J ¼ 13.55 Hz, 4H, ArCH Ar), 4.60 (s, 4H, O-CH ),
2
2
6
4
7
.87 (t, 2H, ArH-calix), 7.04 (d, 4H, ArH-calix), 7.35 (d,
H, ArHN ¼ NZ), 7.58 (s, 2H, ArOH), 7.60 (s, 2H, NH),
1
powder, mp: 2158C (dec). H NMR (CDCl ) d: 2.43 (s, 6H
3
1
3
.82 (s, 4H, ArH-calix), 7.84(d, 4H, ArHZNvNZ).
C
ArZCH ), 3.58 (d, J ¼ 13.51 Hz, 4H, ArCH Ar), 4.10 (d,
3
2
NMR (75 MHz CDCl ): 167.8, 154.8, 151.5, 150.8, 150.5,
3
J ¼ 13.50 Hz, 4H, ArCH Ar), 4.57 (s, 4H, O-CH ), 4.73
2
2
1
1
46.9, 141.0, 131.7, 129.7, 128.1, 126.6, 123.9, 122.6,
24.2, 75.1, 37.7, 31.2, 25.2, 21.5. Anal. calcd for
(s, 4H, NHZCH ), 6.83 (t, 2H, ArH-calix), 7,01 (d, 4H,
2
ArH-calix), 7.07 (m, 2H, ArH-pyridyl), 7.30 (d, 4H,
ArHZNvN), 7.35 (d, 2H, ArH-pyridyl), 7.60 (t, 2H,
ArH-pyridyl), 7.73 (s, 4H, ArH-calix), 7.78 (d, 4H,
ArHZNvN), 8.05 (s, 2H, ArOH), 8.28 (d, 2H, ArH-
C H N O : C, 72.45; H, 5.84; N, 10.14. Found: C, 71.67;
50 48 6 6
H, 5.70; N, 9.97.
Compound 2d: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.49 g (68%) of an orange
1
3
pyridyl) 8.92 (s, 2H, NH). C NMR (75 MHz CDCl3):
167.9, 156.5, 155.1, 151.1, 150.9, 149.4, 146.2, 140.9,
136.7, 131.9, 130.1, 129.9, 129.8, 127.7, 126.6, 123.8,
1
powder, mp: .2568C (dec): H NMR (CDCl ) d: 1,7
3
(
s, 4H, amido-CH ), 3.41 (d, J ¼ 13.52 Hz, 4H, ArCH -
2
2

¨ ¨
O.O. Karaku s¸ and H. Delig o¨ z
1
14
2
5
122.5, 74.7, 45.3, 31.6, 29.7, 21.5. Anal. calcd for
C H N O : C, 72.79; H, 5.48; N, 11.71. Found: C, 72.97;
nitrate in 2 £ 10 M picric acid were vigorously shaken
at 258C for an hour. After the completion of phase
separation, an aliquot of the was withdrawn to record its
UV spectrum. A similar extraction was performed in the
absence of picrate ion in the aqueous solution. Absorbance
5
8 52 8 6
H, 5.59; N, 11.98.
Compound 3d: The solid was eluted with hexane/
ethyl acetate (3:1, v/v) and gave 0.46 g (65%) of a brown
1
powder, mp: 1558C (dec): H NMR (CDCl ) d: 3.60
values have been measured three times at 354 nm (lmax)
spectrophotometrically. The extractability of the metal
cations is expressed by means of the following equation:
3
(
d, J ¼ 13.54 Hz, 4H, ArCH Ar), 3.93 (s, 6H O-CH ), 4.12
2
3
(
d, J ¼ 13.50 Hz, 4H, ArCH Ar), 4.58 (s, 4H, NHZCH ),
2
2
4
.77 (s, 4H, O-CH ), 6.87 (t, 2H, ArH-calix), 7.03 (d, 4H,
2
ArH-calix), 7.04 (d, 4H, ArHZNvN), 7.11 (t, 2H, ArH-
pyridyl), 7.38 (d, 2H, ArH-pyridyl), 7.63 (m, 2H, ArH-
pyridyl), 7.73 (s, 4H, ArH-calix), 7.91 (d, 4H,
ArHZNvN), 8.05 (s, 2H, ArOH), 8.32 (s, 2H, ArH-
A0 2 A
extractabilityð%Þ ¼
where A and A
£ 100;
A0
are the absorbencies with and without
0
1
3
pyridyl), 9.00 (s, 2H, NH). C NMR (75 MHz CDCl3):
ligand, respectively.
1
1
1
68.2, 162.6, 156.9, 155.2, 151.8, 149.7, 147.5, 146.8,
36.8, 133.3, 132.6, 130.1, 128.2, 127.6, 124.1, 123.5,
22.2, 114.1, 74.9, 56.1, 45.9, 31.2.Anal. calcd for
Results and discussion
C H N O Found: C, 70.43; H, 5.30; N, 11.33.Found: C,
5
8 52 8 8
Synthesis and characterisation
7
0.25; H, 5.24; N, 11.16.
Previously, our research group investigated azo coupling
reactions of diketonecalix[4]arenes and triestercalix[4]
arenes with substituted benzene diazonium chlorides (18).
In this study, 12 amidoazocalix[4]arenes have been
synthesised from amido derivatives according to the
method described by Morita et al. (19). Subsequently, their
four telomers were prepared by the synthetic routes
depicted in Scheme 1. All synthesised compounds were
General procedure for the synthesis of telomers
Compound 1a 0.25 g (0.28 mmol) was dissolved in 20 mL
dioxane. Pentaethyleneglycol ditosylate (0.45 mmol) was
added to resulting solution. Ninety-five percent NaH
(
0.34 g, 15 mmol) was added slowly while the solution was
stirring at room temparature for 30 min. The reaction
mixture was followed with TLC and stirring has continued
for 4 days. After evaporating, the solvent dried residue was
washed with petroleum ether and ethanol before acidifying
with 0.1 M HCl. Finally, the precipitated residue was
washed with water and dried in an oven. The solid residue
was purified by column chromatography with ethyl
acetate-methanol as an eluent.
1
13
characterised by UV–vis, FT-IR, H and C NMR
spectroscopic methods as well as elemental analysis
techniques. Some of the compounds were characterised by
2D NMR technique (COSY, HMQC, HMBC, NOESY)
additionally.
Amidocalix[4]arenes (1–3) were synthesised by the
reaction of calix[4]arene diethyl ester and primer aliphatic
amines in toluene/methanol (1:1) under reflux conditions
Telomer T1a: The solid was eluted with ethyl acetate/
methanol (9:1, v/v) and gave 0.1 g (15%) of a red powder,
mp: 120–1308C. MS (MALDI-TOF): m/z 2833
1
13
(Scheme 2). They were characterised by FT-IR, H and
C
NMR spectroscopic techniques. Characteristic amido
þ
[
M þ H] .
C ¼ O stretching bands were observed around
2
1690 cm frequency in FT-IR spectra. The doublet pairs
1
Telomer T1b: The solid was eluted with ethyl acetate/
methanol (9:1, v/v) and gave 0.08 g (10%) of an orange
representing ArCH Ar protons appeared around 3.5 and
2
powder, mp: 1408C. MS (MALDI-TOF): m/z 3143
þ
4.2 ppm of H NMR spectra separately. These peaks
confirm the symmetrical cone conformation amidocalix[4]
arenes in solution. Amido 2NH protons of compounds 1,
2 and 3 were appeared as separate singlet peaks at 8.50,
7.75 and 9.10 ppm on the H NMR spectra, respectively.
The amidoazocalix[4]arene derivatives were gathered
by a coupling reaction of amidocalix[4] arenes (1–3) and
[
M þ H] .
Telomer T1c: The solid was eluted with ethyl acetate/
methanol (9:1, v/v) and gave 0.05 g (10%) of an orange
powder, mp: 2058C. MS (MALDI-TOF): m/z 2839
þ
[
M þ H] .
Telomer T1d: The solid was eluted with ethyl acetate/
methanol (9:1, v/v) and gave 0.15 g (10%) of an orange
diazotized carbocyclic amines in NaNO /HCl (Scheme 3).
2
powder, mp: 1908C. MS (MALDI-TOF): m/z 2903
M þ H]þ.
Each coupling has been selectively accomplished at the
p-position of each calix[4]arene ring to give compounds in
moderate to excellent yields (60–80%). These results are
in accordance with the greater nucleophilicity of the
carbocyclic amine ring The schemed structures of
amidoazocalix[4]arenes were unambiguously confirmed
by their analytical and spectral data.
[
Solvent extraction
A solution (10 mL) of ligand (1 £ 10 M) in chloroform
2
3
2
2
and an aqueous solution (10 mL) of 1 £ 10 M metal

Supramolecular Chemistry
115
O
OHOH
O
CH2
CH2
C O
C O
OC H
OC H
2 5
2
5
(
i)
H N
2
N
(
i)
H N
NH2
CH2
(i)
2
NH2
NH2
O
OHOH O
H C
O
CH2
C O
HN
OHOH
O
CH2
2
O C
HN
C O
CH2
C O
NH
O OH OH
CH2
O
CH2
C O
NH
NH
CH2
CH2
C O
N
N
HN
1
2
3
Scheme 2. Synthesis of amidocalix(4(arenes. (i) Toluene/MeOH (1:1).
The infrared spectrum of each synthesised amidoazo-
calix[4]arene compound presented a strong band at 1495–
triplet, doublet and singlet peaks between 7.9 and 7.0 ppm
for calix[4]arene aromatic protons (Ar–H), a broad peak
between 8.1 and 7.5 ppm for hydroxyl protons (ZOH).
COSY, HMQC, HMBC and NOESY correlations of
some compounds were examined by 2D NMR technique.
Analyses of these correlations also provided important
results about the configuration of compounds.
2
480 cm referring to ZNvNZ. The other y
1
1
around 1268–1250 cm can be assigned to for yC–O.
value
max
2
1
1
The H NMR spectrum of each compound measured in
DMSO-d at 258C showed a pair of doublets between 7.9
6
and 6.9 ppm for substituted aromatic protons (ArH-X),
O
OH OH
O
O
OH OH
O
O
CH2
OHOH
O
CH2
2
CH2
C O
CH2
H C
CH2
C O
2
1
3
C O
NH
C O
O
C
HN
C O
NH
CH2
HN
HN
NH
CH2
R
R
N
N
NaNO \HCl
2
NaNO \HCl
2
R
NH2
NH2
R
R
NaNO \HCl
R
R
2
NH2
R
R
N
N
N
N
N
N
N
R
R
R
N
1
1
1
1
a : –NO2
b : –Br
2
2
a : –NO2
b : –Br
N
N
N
3a : –NO2
b : –Br
N
3
c : –CH3
2c : –CH3
3c : –CH3
O
OH
OH
O
d : –OCH3
O
OH OH
O
2
d : –OCH3
3d : –OCH3
CH2
CH2
H C
CH2
2
O
OH OH
CH2
O
C O
C O
HN
O C
HN
C O
NH
H C
2
NH
O
C
C
O
NH
CH2
NH
CH2
N
N
Scheme 3. Synthesis of amidoazocalix(4(arenes.

¨
O.O. Karaku s¸ and H. Delig o¨ z
¨
1
16
H16
Br
Br
1
0
1
2
3
4
5
6
.0
.0
.0
.0
.0
.0
.0
2
H17
3
4
N
N
N
N
1
2
5
6
1
1
1
8
1
3
7
0
Ha
9
O
OH OH O
NH
7.0
Hb
O
CH2
1
4 CH2
5 C
HN
8
9
1
.0
C
1
O
.0
1
7
NH
0.0
1
6
10.0 9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (t2)
Figure 1. (Colour online) COSY spectrum of amidoazocalix[4]arene 2b.
The COSY spectrum of 2b revealed two noteworthy cross
The most important finding about the conformation of
peaks. One of them can be referred to the interaction between
H16 and H17 protons. While the other one can be assigned to
the interaction between NH and H16 protons (Figure 1).
It is not possible to elucidate the connection between
aromatic rings according to COSY experiment results.
Therefore, construction of the carbon framework was
made possible by the interpretation of a series of selective
INEPT experiments.
amidoazocalix[4]arene 1c was obtained by NOESY
spectra. 2D NOESY spectrum of p-methyphenylazo
substituted amidocalix[4]arene (1c) is presented in
Figure 2. Expanded NOESY spectrum showed that Hb
and OH protons are in the same space because of their
interaction. In the same way, Ha and H12 protons are in the
same space (Figure 2). As a result, we can easily say that
the compound is in cone conformation in solution.
H7
Ht2
OH
H3
0
1
2
3
4
5
6
7
8
9
.0 Ph-CH3
2
2
3
3
3
3
4
.50
.75
.00
.25
.50
.75
.00
.0
.0
.0
.0
.0
.0
.0
.0
.0
Ha
Hb
4.25
4
.50
.75
4
9
.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
8.75
8.50
8.25
8.00
7.75
7.50
7.25
7.00
ppm(t2)
ppm(t2)
Figure 2. (Colour online) NOESY and expanded NOESY spectra for amidoazocalix[4]arene 1c.

Supramolecular Chemistry
117
R
R
R
R
R
N
N
N
N
T1a : –NO2
N
N
N
N
T1b : –Br
Dioxane / NaH
Tos-O-CH (CH OCH ) CH -O-Tos
T1c : –CH3
O
O
CH2
O
O
CH2
2
2
2 4
2
O
OHOH O
CH2
R`
T1d : –OCH3
CH2
C
O
C
C
O
O
C
O
NH
HN
NH
HN
3
R`: CH (CH OCH ) CH
2
2
2
2 4
Scheme 4. Synthesis of telomers.
After the synthesis of amidoazocalix[4]arenes, telomer
derivatives of 1a, 1b, 1c and 1d were synthesized
Absorption properties
The absorption spectra of amidoazocalix[4]arenes (1a–d,
a–d, 3a–d) were recorded in various solvents at
concentrations between 10 and 10 M. The solvents
have been chosen according to their polarities. The visible
absorption spectra of these dyes were found to exhibit
strong solvent dependency in case of the polarity of the
solvents.
(
Scheme 4). These telomers (T1a–T1d) were obtained
2
by reacting 1a, 1b, 1c and 1d with pentaethyleneglycol
ditosylate in dioxane and 95% NaH at room temperature.
Pentaethyleneglycol ditosylate was used for this
polymerisation reaction because it can easily link bulky
azocalix[4]arene molecules with each other.
26
28
Polymerisation reactions were monitored by TLC. The
resulting product mixtures were separated by column
chromatography. The molecular weight data for the
resulting polymers were measured by mass spectrum
analysis. Analysis of the mass spectra showed that each
telomer molecule consists of three calixarene units.
Mass spectrum of telomer T1b is seen in Figure 3. Its
calculated molecular weight is 3188g/mol and its molecular
ion peak is observed as 3143 g/mol. Hence, this result refers
to a telomer molecule with three calixarene units.
The azocalix[4]arene derivatives (1a–d, 2a–d, 3a–d)
showed characteristic absorption patterns. The appearance
of the amidoazocalix[4]arene absorption band at a
relatively high wavelength may be attributed to the
presence of an electron-withdrawing group such as nitro
and bromo groups. The absorption spectrum of some
amidoazocalix[4]arene derivatives exhibited a single
absorption band between 300 and 400 nm and single
shoulder between 400 and 550 nm corresponding to p–p*
and n–p* transitions, respectively. This result is in
Br
Br
Br
B r
B r
Br
N
N
N
N
N
N
N
N
N
N
N
N
O
O
O
O
O
H C
O
O
O
O
O
O
CH
O
OH
O
CH2
O
O
CH2
O HO
O
CH
O
2
CH2
2
2
O
C
O
C
O
C
O
C
O
C
O
C
HN
NH
HN
NH
HN
NH
Figure 3. (Colour online) MALDI TOF spectrum for telomer T1b.

¨ ¨
O.O. Karaku s¸ and H. Delig o¨ z
1
18
Table 1. Absorption maxima (nm) of some compounds in different solutions.
Compound
DMSO
DMF
MeCN
MeOH
MeOH þ KOH
MeOH þ HCl
AcOH
CHCl3
1
1
2
3
a
c
a
d
395
361
400
369
393, 603
358
398, 619
367
382
354
382
362
381
354
382
381
304, 547
470
304, 550
459
382
355
387
363, 508
378
353
379
382
381
355
382
364
accordance with previous diazo calix[4]arene spectra
measured before.
Although the maximum absorption value values
belonging to absorption spectra of compound 3d in
acetonitrile and chloroform are found to be close, lmax
on the spectrum of same compound in MeOH is
observed in longer wavelength values. Spectra of
compound 3d in DMF and DMSO lacks this shift
observed in MeOH.
Solvent effect
Absorption spectra of amidoazocalix[4]arenes were
recorded in six different solvents (DMSO, DMF, MeCN,
CHCl , MeOH and AcOH). Their maximum absorption
3
values were noted in Table 1. Compounds 1a, 1c and 2a
exhibited similar absorption spectra in acetonitrile,
chloroform, methanol and acetic acid solvents. A new
band was observed in DMF on absorption spectra of these
compounds. Bathochromic shifts on the absorption spectra
of these compounds were also observed in DMSO
pH effect
The spectra of compounds 1a, 1c, 2a and 3d in acidic and
basic solutions were recorded by the addition of KOH and
HCl in methanol separately. As expected, there were
bathochromic shifts of maximum absorption values when
KOH was added to the amidoazocalixarenes 1a, 1c, 2a and
(
Figure 4(a)–(c)).
(
a) 2.5
CH CN
3
(
b) 3.00
DMF
CH COOH
3
2
.0
2
2
.5
.0
CHCl3
DMF
CH COOH
3
A
1.5
MeOH
CH CN
3
DMSO
A
1.5
1
0
.0
.5
CHCl3
MeOH
1
0
.0
.5
DMSO
0
.00
0.00
275.0
275.0
400
500
nm
600
700
350
400
450
500
550
nm
(
c) 2.00
(d) 2.50
.0
1.5
MeOH
DMSO
CH CN
3
CHCl3
2
1.5
CH CN
3
DMF
DMSO
DMF
1.0
CH3COOH
A
A
1
0
.0
.5
MeOH
0.5
CHCl3
CH COOH
3
0
.00
0.01
275.0 300
275.0
400
500
nm
600
700
350
400
nm
450
500
Figure 4. (Colour online) UV spectra of amidoazocalix[4]arenes in different solvents: (a) 1a, (b) 1c, (c) 2a (d) and 3d.

Supramolecular Chemistry
119
(
a) 2.00
.5
1.0
.5
(b) 2.00
1c + MeOH
1
a + MeOH
1a + MeOH + KOH
1
1.5
1.0
1c + MeOH + HCl
1c + MeOH + KOH
A
A
1
a + MeOH + HCl
0
0.5
0
.00
2
0.00
75.0
400
500
600
700
800.0
275.0
400
mn
500
600.0
mn
(
c) 2.00
2a + MeOH
(d) 2.00
1.5
2a + MeOH + KOH
3d + MeOH
1.5
2a + MeOH + HCl
A
1.0
A
1.0
0.5
3d + MeOH + KOH
3d + MeOH + HCl
0.5
0
.00
2
0.00
75.0
400
500
600
700
800.0
275.0
400
500
600 650.0
mn
mn
Figure 5. (Colour online) UV spectra of amidoazocalix[4]arenes in acidic and basic solvents: (a) 1a, (b) 1c, (c) 2a (d) and 3d.
3
d (Figure 5(a)–(d)). This is due to the easiness in
turned into purple at pH 10 as expected. The colour
changes have been observed on compound 3d solutions at
pH 1 and pH 14 (Figures 6 and 7).
deprotonation of the lower rim hydroxyl groups by the
basic solvent. This deprotonation phenomenon is showed
in Scheme 5. No shift on the absorption spectra of the
compounds 1a, 1c and 2a was observed when HCl was
added to methanol. However, compound 3d exhibited two
absorption bands at 363 and 508 nm when HCl was added
in methanol controversially. This extra absorption band
appearing at a longer wavelength can be explained by the
protonation of the nitrogen atom on the pyridyl ring.
The results of pH effect experiments were observed as
colour changes on the solutions of compounds in different
pH by the ‘naked eye’. The yellow colour of compound 2a
Extraction properties
Transportation experiments with metal picrate salts were
carried out with a H OZCHCl liquid–liquid phase
2
3
transfer system using the amidoazocalix[4]arenes as cation
carriers. The results of the cation transportation exper-
iments are in harmony with those of the two-phase
extraction measurements.
The ionophoric properties of azo compounds (1a–d,
a–d, 3a–d) and telomer derivatives (T1a–T1d) towards
2
the alkaline (Na , K ), alkaline-earth (Sr ) and the
þ
þ
2þ
NO2
O N
NO2
O2N
þ
þ
2þ
2þ
2þ
2
transition metal cations (Ag , Hg , Hg , Co , Ni ,
3þ
2
Cu , Cd , Pd , Cr
þ
2þ
2þ
3þ
and Al ) were initially
investigated by the picrate extraction method (20). The
results are expressed in units of percentages of cation
extracted (E%)and presented in Tables 2 and 3 and
Figures 8 and 9.
N
N
N
N
N
N
N
N
Base
þ
þ
2þ
3þ
According to the results, Ag , Hg , Hg and Cr
O–
O–
O
O
O
CH2
C
NH
O
OHOH
metal cations were transported with high efficiency by
synthesised compounds. Extraction reactions of telomer
structures took place with higher efficiency rates with
respect to those of monomer structures. Memon and
coworkers also studied metal extraction of calixarene
monomers and telomers. They observed selectivity for
CH2
CH2
C O
CH2
O
C
O
C
HN
O
NH
HN
Scheme 5. Ionisation equilibrium of the compound 1a in basic
solution.

¨
O.O. Karaku s¸ and H. Delig o¨ z
¨
1
20
pH=1 pH=2 pH=3 pH=4 pH=5 pH=6 pH=7 pH=8 pH= 9 pH=10 pH=11 pH=12 pH=13 pH=14
Figure 6. (Colour online) Solutions of compound 2a in different pH.
pH=1 pH=2 pH=3 pH=4 pH=5 pH=6 pH=7 pH=8 pH=9 pH=10 pH=11 pH=12 pH=13 pH=14
Figure 7. (Colour online) Solutions of compound 3d in different pH.
a
Table 2. Extraction of metal picrates with ethylene amidoazocalix[4]arenes and their telomer derivatives .
Picrate salt extracted (%)
þ
þ
2þ
þ
þ
2þ
2þ
2þ
2þ
2þ
2þ
3þ
3þ
Al
Na
K
Sr
Ag
Hg
Hg
Co
Ni
Cu
Cd
Pb
Cr
1
1
1
1
T1a
T1b
T1c
T1d
a
b
c
0.0
0.0
5.5
47.5
17.5
25.3
28.2
55.6
0.0
0.0
7.5
44.6
15.3
14.2
21.6
51.6
08
4.7
10.3
41.6
40.1
54.1
36.2
61.9
86.1
95.7
25.1
41.4
42.3
56.6
89.3
87.9
94.7
95.3
24.2
46.9
47.7
63.2
85.8
89.9
96.2
92.5
1.5
12.5
22.5
31.2
22.5
27.3
38.1
43.6
2.8
3.2
1.5
10.7
24.0
43.5
21.4
33.5
47.2
53.8
2.1
6.5
3.2
11.0
33.7
33.2
52.1
47.4
65.2
76.6
84.2
6.3
24.4
33.0
51.5
23.4
35.2
51.5
57.3
19.0
26.1
49.5
14.2
34.6
38.7
57.02
19.9
41.4
14.6
26.6
44.8
53.2
10.6
29.5
11.6
24.1
34.7
33.0
19.5
45.9
17.5
27.9
37.5
42.5
d
a
25
23
22
Note:
a # ^ 2%.
H
2
O/CHCl
3
¼ 10/10 mL (v/v): [picric acid] ¼ 2 £ 10 M, [ligand] ¼ 1 £ 10 M, [metal nitrate] ¼ 1 £ 10 M; 298 K, 1 h contact time.
2
þ
2þ
2þ
Hg , Cd and Pb in different molecules. Results of this
study are in consistent with those of interested study (21).
Cations are believed to hold an encapsulation into the
cavity defined by the conjugated chromophore azo
bear hard nitrogen donor atoms. Although they display
þ
a weak affinity towards soft metal cations such as Ag ,
2
þ
they exhibit respectively higher affinity towards Hg
cation.
(
ZNvNZ) groups. p- Interactions may play important
role in complexation with amidoazocalix[n ]arenes.
Compounds 2a–d and 3a–d were synthesised with
1,4-diaminobutane and 2-amino-methylpyridine, respect-
ively, to determine the effect of cyclic and free amide
Results of this study have shown that interested compounds
a
Table 3. Extraction of metal picrates with amidoazocalix[4]arenes .
Picrate salt extracted (%)
þ
b.þ
2þ
þ
þ
2þ
2þ
b.2 þ
2þ
2þ
2þ
3þ
3þ
Al
Na
K
Sr
Ag
Hg
Hg
Co
Ni
Cu
Cd
Pb
Cr
2
2
2
2
3
3
3
3
a
b
c
d
a
b
c
0.0
5.5
42.1
1.6
0.5
6.1
4.2
3.8
0.0
2.1
4.9
41.5
0.9
1.8
6.9
3.0
0.0
1.9
6.8
30.4
1.5
1.6
6.7
3.2
4.6
3.4
4.7
54.3
19.6
92.3
93.9
91.0
19.2
18.6
19.4
55.3
37.7
63.8
66.0
60.0
24.8
24.5
29.5
76.4
34.6
88.6
93.2
93.0
0.9
1.5
5.1
28.4
1.5
1.9
6.4
1.3
1.2
3.6
4.3
33.2
2.1
2.5
6.6
1.4
2.0
4.0
5.9
44.7
12.4
30.8
33.1
10.3
0.6
2.9
5.7
37.2
5.6
3.4
8.1
3.9
6.1
6.9
9.0
37.8
15.4
13.7
11.2
15.2
10.6
12.2
13.7
63.6
13.4
39.0
30.4
30.8
8.8
11.9
11.5
51.0
20.1
21.8
16.0
14.4
d
a
25
23
22
Note:
a # ^ 2%.
H
2
O/CHCl
3
¼ 10/10 mL (v/v): [picric acid] ¼ 2 £ 10
M, [ligand] ¼ 1 £ 10 M, [metal nitrate] ¼ 1 £ 10 M; 298 K, 1 h contact time.

Supramolecular Chemistry
121
Figure 8. (Colour online) Extraction percentages of monomers and telomers.
Figure 9. (Colour online) Extraction percentages of butyl and pyridyl amidoazocalix[4]arenes.
groups on the extraction phenomenon. Their extraction
efficiencies were noted in Table 3.
Extraction efficiencies of butylene amido compounds
concentrations are reached. The colour change of
compound 2a at pH 10 and that of compound 3d at pH 1
and 14 are clearly visible to the ‘naked eye’. This allowed
us to use the interested compounds as indicators.
(
2a–2d) and pyridyl amido compounds (3a–3d) were also
graphed in Figure 9. The extraction efficiencies of
telomers T1a–T1d were found to be more than twice of
those of monomers 1a–d, respectively. The extraction
efficiencies of cyclic amido derivatives (2a–2d) were
observed to be less than those of amido pyridyl derivatives
Extraction studies of amidoazocalix[4]arene com-
pounds 1a, 2a and 3a exhibited poor binding abilities
towards metal cations. This feature may result from the
strong electron withdrawing properties of the substituted
nitro groups. Pyridylamido group containing amidoazo-
calix[4]arene compounds 3b, 3c and 3d exhibited
high extraction efficiencies towards heavy metal ions
(
3a–3d). This result can be explained by two features.
It may be resulted from the space of calix[4]arene moiety.
It also may be resulted from the electron density of the
pyridyl group and its flexibility. The second feature ends
up with a significant contribution for extraction.
þ
þ
2þ
(Ag , Hg , Hg ). This result can be explained with
high electron density of substituted pyridyl groups
and their elastic structure in solution. Extraction results
of this study indicate that the mechanism of complexa-
tion depends on the interaction between metal cations
and both amido and azo groups of the calix[4]arene
units.
Conclusion
The 12 novel amidoazocalix[4]arene (1a–d, 2a–d, 3a–d)
compounds and some of their telomer derivatives were
synthesised and characterised. Absorption and extraction
properties of synthesised compounds were investigated.
Amidoazocalix[4]arene compounds 1a, 1c, 2a and 3d
exhibited great binding abilities to various bases
The selective tendencies of synthesised compounds 3b,
3c and 3d through complexation with heavy metal ions
1
1
21
(Ag , Hg , Hg ) may be of considerable importance for
the future design of novel calix[n]arene based receptors,
carriers or supramolecular structures. The results of the
ongoing research studies orienting chemosensation and
dyeing properties of these new amidoazocalix[4]arenes will
be presented in the future.
(
MeOH þ KOH) in an equivalent stoichiometry with
colorimetric changes. The binding feature of synthesised
compounds can be assigned to hydrogen bonding and
deprotonation of the interested compounds. The binding
phenomenon did not take place until high base
1
13
Supporting Information H and C NMR spectra for
the compounds prepared.

¨
O.O. Karaku s¸ and H. Delig o¨ z
¨
1
22
Acknowledgements
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We thank to the TUBITAK (Center of Science and Technology
Research of Turkey) (Project No: 107T770) and BAP (Scientific
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financial supports of this work. We also thank to Assoc. Prof.
Cavit KAZAZ (Atat u¨ rk University) for the 2D NMR spectra
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