Synthesis and properties of calix[4]arene telluropodant ethers as Ag + selective sensors and Ag+, Hg2+ extractants

Article abstract of DOI:10.3762/bjoc.5.59

Three novel phenyltelluroalkoxyl functionalized tweezer-like calix[4]arenes 6-8 and two monophenyltelluropropoxyl functionalized calix[4]arenes 10 (cone conformer) and 12 (partial cone conformer) were synthesized and characterized. They are good Ag^+<

Full text of DOI:10.3762/bjoc.5.59

Synthesis and properties of calix[4]arene
telluropodant ethers as Ag+ selective sensors and
Ag+, Hg2+ extractants
Yang Lu1, Yuanyuan Li1, Song He1, Yan Lu1, Changying Liu2,
Xianshun Zeng*1,2 and Langxing Chen*2
Full Research Paper
Open Access
Address:
Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
1Key Laboratory of Display Materials and Photoelectric Devices
(Tianjin University of Technology), Ministry of Education, Tianjin
300384, P.R. China and 2State Key Laboratory of Elemento-Organic
Chemistry, Nankai University, Tianjin 300071, P.R. China
doi:10.3762/bjoc.5.59
Received: 04 July 2009
Accepted: 09 September 2009
Published: 28 October 2009
Email:
Xianshun Zeng* - xshzeng@eyou.com; Langxing Chen* -
lxchen@nankai.edu.cn
Editor-in-Chief: J. Clayden
© 2009 Lu et al; licensee Beilstein-Institut.
License and terms: see end of document.
* Corresponding author
Keywords:
calix[4]arenes; extractants; mercury; sensors; silver; telluropodant
ether
Abstract
Three novel phenyltelluroalkoxyl functionalized tweezer-like calix[4]arenes 6–8 and two monophenyltelluropropoxyl functional-
ized calix[4]arenes 10 (cone conformer) and 12 (partial cone conformer) were synthesized and characterized. They are good Ag+-
selective ionophores in ion-selective electrodes evaluated by electromotive force measurements of polymer membrane electrodes.
The tweezer-like ionophores 6–8 showed excellent extraction ability towards Ag+ and Hg2+.
Introduction
There is much interest in the development of compounds that tions, enrichment, and analyses of ionic and neutral molecular
selectively respond to specific metal ions for use as ion sensors. species [1-4]. In particular, the ion-selective electrode (ISE) is
As the third generation of supramolecule, benefiting from their an important target in analytical applications [5-10]. To
three-dimensional structures and easy chemical modification improve the ion selectivity of calixarenes, a great deal of effort
both at the upper- and lower-rims as well as their potential has been devoted to the design and synthesis of novel function-
receptor properties for cations, anions and neutral molecules, alized calixarenes in recent years [1-4]. In fact, a large number
calixarenes have enjoyed widespread use in various areas of of calixarene derivatives containing pendant ether, amide,
science and technology. One of their successful applications as ketonic, ester and crown ether groups have been employed in
sensors is in analytical chemistry. They are useful for separa- studies of ISEs sensitive to sodium ions [11-20], potassium ions
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Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
[21-25], caesium ions [26-30], thallium ions [31], lead ions [32, prepared in situ by the reaction of diphenylditelluride with
33] and organic ammonium ions [34-36]. But only a few reports sodium borohydride in the presence of NaOH at the reflux tem-
are concerned with calixarenes as carriers sensitive to transition perature of ethanol–benzene (1:1, v/v). The structure and con-
metal ions in the ionophore-based ISEs [30,37]. Due to their formation of compounds 6–8 could be conveniently determined
large covalent radius and greater polarizability compared to by their proton magnetic resonance spectra. As seen from 1H
oxygen, the coordinating chemistry of heavier Group 16 NMR data of 6–8, the methylene bridge protons of the calix
analogues (S, Se, Te), especially sulfur, has attracted consider- skeleton appeared as two doublets at nearly 4.25 ppm and 3.27
able interest in the chemical community. A number of ligands ppm and the signals of the calix aromatic protons and the upper-
including pendant thioethers and crown thioethers with different rim tert-butyl protons were separated as two singlet peaks in a
denticity have been synthesized and their metal ion chemistry 1/1 integration ratio, which all indicated that they are in cone
studied, producing a diverse range of structures and unpreced- conformation [56,57]. The methylene protons in the pendant
ented electronic and redox response [38-49]. However, the use region gave rise to different chemical shifts depending on the
of the tellurium atoms as soft donors to design sensors and distance from O atoms or Te atoms, for example, those at-
investigation of their ion selective performances have not been tached to the O atom appeared at 4.02–3.94 ppm and those
described to date. Aiming to construct receptor molecules close to the Te atom were found at 3.38–2.98 ppm. In addition,
which are sensitive to transition metal ions, a large number of 13C NMR spectrum afforded some information about the influ-
calix[4]arene derivatives containing N, S, Se and P(III) atoms ence of tellurium: the phenyl carbons attached to Te atoms were
as soft donors have been prepared and their sensor properties recorded at 111.79–111.57 ppm, while the signals of saturated
have also been evaluated by ion-selective electrodes (ISEs) in carbons attached to Te atoms were detected at 8.60–4.88 ppm.
our group and by our co-workers [50-53]. To continue our
interest in the development of new ionophores, herein we The cone and partial cone conformers of calix[4]arenes 10
describe the design and synthesis of three novel tweezer-like (cone) and 12 (partial cone) were synthesized by the reaction of
25,27-dihydroxy-26,28-bis(phenyltelluroalkoxy)calix[4]arenes the cone and partial cone conformers of calix[4]arenes 9 and 11
6–8 composed of two tellurium atoms on the lower rims linked with the sodium salt of phenyl tellurate in 93% and 71% yields,
via methylene groups respectively, and study their Ag+- respectively (Scheme 2). Their structures were determined by
selective behavior by electromotive force measurements of 1H NMR and MS spectra. The phenyl carbon resonances at-
polymer membrane electrodes.
tached to tellurium atoms were found at 112.08 ppm and 112.04
ppm, respectively. The signals of saturated carbons attached to
tellurium were detected at 4.06 ppm and 3.54 ppm, respectively.
Results and Discussion
Synthesis and conformations of calix[4]arene
Ion selectivity
6–8, 10 and 12
For assessment of Ag+ ion selective behaviour of phenyltelluro-
alkoxyl modified calix[4]arenes derivatives (6–8, 10 and 12),
ISEs based on 6–8, 10 and 12 as ionophores were prepared and
their selectivity coefficients for Ag+ cations were investigated
As shown in Scheme 1, the calix[4]arenes 6–8 were synthe-
sized in yields between 92% and 97% by the reaction of the
preorganized cone conformation calix[4]arene dibromides 3–5
[54,55] with the sodium salt of phenyltellurate, which was
Scheme 1: Synthesis and structures of calix[4]arenes 6–8; 3, 6: n = 2; 4, 7: n = 3; 5, 8: n = 5.
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Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
Scheme 2: Synthesis of calix[4]arene 10 and 12.
against alkali metal, alkaline-earth metal, lead, ammonium ions were between 49.4 ± 3.6 and 55.4 ± 1.3 mV·decade−1 to the
and some transition metal ions using the fixed interference activity of Ag+ ion within the activity range 10−5.3–10−2.0 M
method (FIM) [54,55]. Firstly, the response characteristics of AgNO3, which indicated that all of calix[4]arenes 6–8, 10 and
Ag+-ISEs based on different ionophores were tested. It was 12 were good ionophores for Ag+-ISEs.
noted that the Nernstian slopes of 6–8, 10 and 12 based ISEs
Table 1: Selectivity coefficients (logK
) of the electrodes based on ionophores 6–8, 10 and 12.a
logK
ion
6
7
8
10
12
Ag+
Na+
0
0
0
0
0
−4.0
−3.9
−3.7
−4.5
−4.4
−4.1
−3.8
−4.1
−4.4
−4.0
−1.5
−4.0
−3.6
−4.1
−4.4
−4.2
−4.1
−3.9
−3.8
−3.9
−3.9
−1.8
−3.7
−3.5
−4.2
−4.3
−4.5
−4.1
−3.8
−4.0
−4.0
−4.0
−1.5
−3.8
−3.8
−3.5
−4.2
−4.5
−3.6
−3.3
−3.8
−3.8
−3.7
−1.4
−4.2
−4.1
−4.3
−5.2
−5.2
−5.1
−5.3
−5.3
−5.0
−4.9
−1.8
K+
NH4+
Mg2+
Ca2+
Zn2+
Cu2+
Ni2+
Cd2+
Pb2+
Hg2+
aThe representative electrochemical cell for the EMF measurement was as follows: Ag·AgCl | int. soln. (0.01 M KCl) | PVC membrane | sample | salt
bridge (3 M KCl) | saturated KCl | Hg2Cl2·Hg.
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Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
Furthermore, the Ag+ selectivity of phenyltelluride functional- the calix aromatic π system was recognized as an assistant
ized calix[4]arene 6–8, 10 and 12 was evaluated by the poten- donor instead of phenolic oxygen atoms to bind cations [60-64],
tiometric selectivity coefficients (logK
) (Table 1). As their binding ability towards metal ions unavoidably decreased
shown in Table 1, the polymer membranes containing in this experiment. Therefore, calix[4]arene 12 exhibited higher
calix[4]arenes 6–8, 10 and 12 as ionophores gave excellent Ag+ selectivity due to its lower binding ability mainly towards
logK
values (≤−3.3) against most of the interfering cations Mg2+, Ca2+, Ni2+, Zn2+, Cu2+, Cd2+ and Pb2+.
examined (i.e., Na+, K+, NH4+, Mg2+, Ca2+, Ni2+, Zn2+, Cu2+,
Cd2+ and Pb2+), except that Hg2+ exhibited relatively lower dis- Extraction behaviors
crimination (logK
≤−1.4) compared with other interfering The extraction ability of tweezer-like receptors 6–8 for alkali,
cations being examined. It is known that the smaller the alkaline earth metals, lead, ammonium and some of transition
logK
value, the greater the electrode preference for the metal cations was measured by Pederson’s method. The data are
primary ion over the interfering ions [54]. In other words, the summarized in Table 2. For comparison, the cone and partial
lower value of selectivity coefficient obtained in present 6–8-, cone conformers of calix[4]arenes 10 and 12 were examined
10- and 12-based ISEs illustrated their high Ag+ selectivity and under the same conditions. As can be seen from Table 2, most
only weakly response to the above interfering ions. The strong of the receptors showed very weak extraction ability towards
Hg2+ interference, once observed in some of ionophore-based Li+, Na+, K+, Ca2+, which meant that these ionophores had
ISEs [54] and traditional Ag2S-based [58,59] ISE is largely weak affinity for these main Group cations. It was noteworthy
eliminated in the present of ISEs (logK
≤−1.4). It is that the soft Ag+ and Hg2+ ions were almost quantitatively
reasoned that those ions with high hydration energies, such as extracted by calix[4]arenes 6–8. The cone conformer 10 exhib-
Na+, K+, NH4+, Ca2+, Mg2+, Pb2+ and most of divalent transi- ited strong extraction ability towards Hg2+ and moderate extrac-
tion metal ions, can not strongly interact with tellurium donors tion ability towards Ag+. However, the partial cone conformer
in the ionophores, while less heavily hydrated soft Ag+ ion 12 just gave moderate extraction ability towards Hg2+ and weak
could coordinate to soft tellurium donors selectively. Another extraction ability towards Ag+. Thus, the extraction ability of
interesting observation was that for 12-based ISEs, the dis- the receptor 6–8, 10 and 12 towards Ag+ and Hg2+ was given in
crimination of Mg2+, Ca2+, Ni2+, Zn2+, Cu2+, Cd2+ and Pb2+ is the following order: Te2 (6–8) > Te (10, cone conformer) > Te
almost one order of magnitude larger than those of 6–8- and (12, partial cone conformer). This sequence revealed that the
10-based ISEs. The weak binding ability of 12-based ISEs soft tellurium donors play a key role in the binding with the soft
towards Mg2+, Ca2+, Ni2+, Zn2+, Cu2+, Cd2+ and Pb2+ maybe Ag+ and Hg2+ cations and the phenolic oxygen atoms on the
explained by the fact that the monophenyltelluropropoxyl lower-rim may involve in the complexation with Ag+ and Hg2+
substituted group was inverted to the upper rim of 12 due to its as assistant donors. These observations further proved that the
partial cone conformation (Scheme 2), which made phenolic cone conformation of calix[4]arene was much more favorable
oxygen (once cooperating with tellurium atom to bind metal molecular framework for binding metal ions than correspond-
ions) difficult to interact with cations simultaneously. Although ing partial cone conformation. In other transition metal ions
Table 2: The percentage of metal picrates extracted from the aqueous to the organic phase by calixarenes 6–8, 10, and 12.
ion
Extraction percentage (%)
6
7
8
10
12
Li+
12.8
0.9
11.8
0.9
1.7
1.1
2.3
Na+
K+
0.7
0.5
5.4
0
1.0
0
0.5
0.5
Ca2+
Cu2+
Mn2+
Cd2+
Ni2+
Zn2+
Pb2+
Hg2+
Ag+
5.8
3.9
4.1
0.8
1.2
25.1
29.9
23.7
33.3
42.9
25.7
100
100
18.6
34.7
16.8
43.5
39.3
18.4
89.8
100
19.0
20.1
20.0
30.8
35.5
28.6
98.6
100
16.6
19.5
34.6
28.7
27.5
8.7
11.8
7.8
7.9
20.6
17.0
9.2
86.4
68.3
51.8
21.2
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Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
cases such as Ni2+, Zn2+, Mn2+, Cu2+ and Cd2+, the receptors water (100 ml). The mixture was extracted three times with
6–8 and cone conformer 10 showed weak to moderate extrac- chloroform. The combined extracts were washed thoroughly
tion ability (extraction% = 16.8–43.7%). But the extraction with water and dried over anhydrous sodium sulfate. The dry
ability of partial cone conformer 12 towards these ions is much solution was filtered. The filtrate was evaporated to dryness
weaker than those of receptors 6–8 and 10. Based on the better under vacuum. The oily residue was purified by chromatog-
performance of receptor 10 compared with corresponding raphy on silica gel with (CH2Cl2/petroleum ether v/v, 1/3) to
analogue 12, it was further confirmed that the binding ability of give 6 as a white powder in 97% yield. FAB+-MS m/z 1139.9
phenolic oxygen donors on the lower rim of ligand 10 towards (M+, Calcd, 1139.8). 1H NMR: 7.75 (d, 4H, J = 6.6 Hz,
Ni2+, Zn2+, Mn2+, Cu2+ and Cd2+ was much stronger than those Te–Ph–H), 7.70 (s, 2H, OH), 7.23–7.16 (m, 6H, Te–Ph–H),
of the calix aromatic π system of ionophore 12, which is in 7.02 (s, 4H, Ar–H), 6.82 (s, 4H, Ar–H), 4.24 (d, 4H, J = 12.8
accordance with the complexation behavior in the ISEs though Hz, ArCH2Ar), 4.02 (t, 4H, J = 5.7 Hz, OCH2CH2), 3.38 (t, 4H,
the solvent systems are significantly different.
J = 6.4 Hz, TeCH2CH2), 3.29 (d, 4H, J = 12.8 Hz, ArCH2Ar),
2.34 (m, 4H, CH2), 1.26 (s, 18H, t-Bu–H), 0.98 (s, 18H,
t-Bu–H). 13C NMR: 150.66, 149.49, 146.91, 141.38, 138.30,
Conclusion
In summary, three novel phenyltelluroalkoxyl functionalized 132.63, 129.12, 127.59, 127.47, 125.53, 125.07, 111.62, 76.82,
tweezers-like calix[4]arenes 6–8 and two monophenyltelluro- 33.87, 33.77, 31.97, 31.69, 31.00, 4.88. Anal. Calcd. for
propoxyl functionalized calix[4]arenes 10 (cone conformer) and C62H76O4Te2: C, 65.30; H, 6.72. Found: C, 65.22; H, 6.79.
12 (partial cone conformer) were synthesized and characterized.
25,27-Dihydroxy-26,28-bis(phenyltelluro-
Potentiometric selectivity evaluation showed that they are good
butoxy)-5,11,17,23-tetra-tert-
butylcalix[4]arene 7
Ag+-selective ionophores in ISEs. The tweezer-like ionophores
6–8 showed excellent extraction ability towards Ag+ and Hg2+.
Their structure–selectivity relationships and comparative exper-
iments with other ionophores containing S and Se donors are
now being investigated and will be reported in due course.
Compound 7 was synthesized as yellowish oil in 96% yield.
FAB+-MS m/z 1167.6 (M+, Calcd, 1167.8). 1H NMR: 7.75 (d,
4H, J = 6.2 Hz, Te–Ph–H), 7.56 (s, 2H, OH), 7.23–7.11 (m, 6H,
Te–Ph–H) 7.02 (s, 4H, Ar–H), 6.79 (s, 4H, Ar–H), 4.21 (d, 4H,
J = 13.0 Hz, ArCH2Ar), 3.94 (t, 4H, J = 5.7 Hz, OCH2CH2),
3.27 (d, 4H, J = 13.0 Hz, ArCH2Ar), 3.07 (t, 4H, J = 6.8 Hz,
TeCH2CH2), 2.07 (m, 8H, CH2CH2), 1.27 (s, 18H, t-Bu–H),
0.96 (s, 18H, t-Bu–H). 13C NMR: 150.60, 149.73, 146.59,
141.16, 138.28, 132.44, 128.99, 127.59, 127.34, 125.32, 124.88,
111.57, 75.47, 33.74, 32.03, 31.60, 30.89, 28.32, 8.30. Calcd.
for C64H80O4Te2: C, 65.78; H, 6.90. Found: C, 66.01; H, 6.79.
Experimental
General Remarks
Melting points were determined with a Boetius Block appar-
atus. 1H NMR spectra were recorded on a Bruker AC-P200
spectrometer at 200 MHz in CDCl3 solution, using tetramethyl-
silane as an internal standard. 13C NMR spectra were recorded
on a Bruker AC-P200 spectrometer at 50 MHz in CDCl3 solu-
tion. Elemental analyses were performed on a Perkin-Elmer
2400C instrument. Mass spectra were recorded on a VG ZAB-
HS spectrometer. Compounds 3–5 [54,55] and 9 and 11 [50-53]
were prepared according to literature procedures.
25,27-Dihydroxy-26,28-bis(phenyltelluro-
hexoxy)-5,11,17,23-tetra-tert-
butylcalix[4]arene 8
Compound 8 was synthesized as yellowish oil in 92% yield.
FAB+-MS m/z 1223.7 (M+, Calcd, 1223.9). 1H NMR: 8.10 (s,
2H, OH), 7.73 (d, 2H, J = 6.3 Hz, Te–Ph–H), 7.71 (d, 2H, J =
6.3 Hz, Te–Ph–H), 7.58 (m, 3H, Te–Ph–H), 7.18 (m, 3H,
25,27-Dihydroxy-26,28-bis(phenyltelluro-
propoxy)-5,11,17,23-tetra-tert-
butylcalix[4]arene 6
Diphenyl ditelluride (512 mg, 1.25 mmol), prepared from Te–Ph–H), 7.02 (s, 4H, Ar–H), 6.81 (s, 4H, Ar–H), 4.25 (d, 4H,
phenyl Grignard reagent with tellurium powder in 78% yield, J = 12.8 Hz, ArCH2Ar), 3.98 (t, 4H, J = 6.2 Hz, OCH2CH2),
was dissolved in ethanol (30 ml) and benzene (30 ml) in a 3.27 (d, 4H, J = 12.8 Hz, ArCH2Ar), 2.98 (m, 4H, TeCH2CH2),
100 ml round-bottomed flask. Under an atmosphere of nitrogen, 1.98–1.55 (m, 16H, –(CH2)4–), 1.31 (s, 18H, t-Bu–H), 0.97 (s,
solid sodium borohydride (228 mg, 6 mmol) was added in small 18H, t-Bu–H). 13C NMR: 150.73, 149.67, 146.57, 141.19,
portions to the solution until the orange color of the diphenyl 138.12, 132.61, 129.02, 127.76, 127.32, 125.39, 124.98, 111.79,
ditelluride disappeared. The rest of the sodium borohydride was 76.20, 33.77, 31.69, 30.99, 29.79, 25.23, 8.60. Calcd. for
added in one portion. The colorless solution was heated to C68H88O4Te2: C, 66.69; H, 7.24. Found: C, 66.59; H, 7.28.
reflux. A solution of calix[4]arene dibromide 3 (1 mmol) in
benzene (20 ml) was added. The reaction mixture was heated at
reflux for 1 h, cooled to room temperature, and poured into
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Beilstein Journal of Organic Chemistry 2009, 5, No. 59.
General procedure for the synthesis of ditel-
lurocalix[4]arenes 10 (cone) and 12 (partial
31.55, 29.78, 23.21, 19.20, 10.49, 3.54. Calcd. for C59H78O4Te:
C, 72.40; H, 8.03. Found: C, 72.66; H, 8.18.
cone)
Diphenyl ditelluride (128 mg, 0.31 mmol) was dissolved in
ethanol (10 ml) and benzene (20 ml) in a 50 ml round-bottomed
flask. Under an atmosphere of nitrogen, solid sodium boro-
hydride (57 mg, 1.5 mmol) was added in one portion. The
orange solution was heated to reflux for one hour. Then, a solu-
tion of calix[4]arene monobromide (214 mg, 0.25 mmol) in
benzene (5 ml) is added. The reaction mixture was heated at
reflux for 1 h, cooled to room temperature, and poured into
water (40 ml). The mixture was extracted with chloroform for
three times. The combined extracts were washed thoroughly
with water and then dried over anhydrous sodium sulfate. The
dry solution was filtered. The filtrate was evaporated to dryness
under vacuum. The oily residue was purified by column chro-
matography.
EMF Measurements. All EMF (electromotive force) measure-
ments were made at 25 °C, using a pH/mV meter. The sample
solution was magnetically stirred and kept in a thermostatted
water bath. The EMF values were corrected by subtracting the
liquid-junction potential between the external reference elec-
trode and the sample solution in the higher Ag+ concentration.
Selectivity coefficients. The potentiometric selectivity coeffi-
cient, K
, determined here is defined by the
Nikolsky–Eisenman Equation (Equation 1).
(1)
where E represents the experimentally observed potential, R the
gas constant, T the thermodynamic temperature in K, F the
Faraday constant, aAg the Ag+ activity, aM the activity of the
interfering cation, and ZM the charge of the interfering cation.
The selectivity coefficients were determined by a mixed-solu-
tion method [65,66]. In this mixed-solution method, the concen-
tration of silver ion is varied while that of the interfering ions
such as Na+, K+, NH4+, Ca2+, Mg2+ are 0.1 M; Zn2+, Cu2+,
Ni2+, Cd2+, Pb2+, Hg2+ are 0.01 M. According to this method,
25-Hydroxy-26,28-dipropoxy-27-(3-phenyl-
telluropropoxy)-5,11,17,23-tetra-tert-butyl-
calix[4]arene 10 (cone)
Calix[4]arene 10 is obtained as yellowish oil in 93% yield (228
mg). FAB+-MS m/z 978.0 (M+). 1H NMR: 7.45 (d, 2H, J = 7.2
Hz, Te–Ph–H), 7.25–7.18 (m, 3H, Te–Ph–H), 7.15 (s, 2H,
ArH), 7.02 (s, 2H, ArH), 6.51 (s, 2H, ArH), 6.46 (s, 2H, ArH),
4.18 (d, 2H, J = 12.9 Hz, ArCH2Ar), 4.16 (d, 2H, J = 12.9 Hz,
ArCH2Ar), 4.05–3.75 (m, 6H, OCH2), 3.20 (d, 2H, J = 12.9 Hz,
ArCH2Ar), 3.17 (d, 2H, J = 12.9 Hz, ArCH2Ar), 1.89–1.78 (m,
4H, CH2CH2Te), 1.33 (s, 9H, t-Bu–H), 1.31 (s, 18H, t-Bu–H),
0.97 (t, 6H, J = 9.1 Hz, CH2CH3), 0.79 (s, 9H, t-Bu–H). 13C
NMR: 153.76, 151.64, 150.79, 145.73, 145.03, 141.30, 138.47,
135.97, 132.09, 131.82, 129.13, 127.40, 125.67, 124.98, 124.81,
124.66, 112.08, 75.82, 34.13, 33.81, 33.65, 31.74, 31.38, 31.07,
23.41, 10.76, 4.06. Calcd. for C59H78O4Te: C, 72.40; H, 8.03.
Found: C, 72.45; H, 8.08.
the potentiometric selectivity coefficients, K
, can be evalu-
ated from the potential measurements on solutions containing a
fixed concentration of the interfering ions (Mn+) and varying
the concentration of Ag+ ion using Equation 2.
(2)
The resulting logK
values are summarized in Table 1.
Extraction experiments. Extraction experiments were carried
out using a solution of metal picrate in water saturated with
dichloromethane (1.00 × 10−4 mol·L−1) and solutions of the
ligand in water saturated with dichloromethane (1.00 × 10−3
mol·L−1). Equal volumes (0.01 L) of the mutually saturated
solvents containing the metal ion salt in the aqueous phase and
the ligand in the organic phase were shaken for 30 min by 2D-2
oscillator and then left for 2 h at (25 ± 0.05) °C. For the deter-
mination of picrates in water phase, a cary-300 UV-visible
spectrophotometer was used and absorbance readings were
taken at 354 nm.
25-Hydroxy-26,28-dipropoxy-27-(3-phenyl-
telluropropoxy)-5,11,17,23-tetra-tert-butyl-
calix[4]arene 12 (partial cone)
Compound 12 is synthesized as yellowish oil in 71% yield.
FAB+-MS m/z 978.2 (M+). 1H NMR: 7.65 (d, 2H, J = 7.4 Hz,
Te–Ph–H), 7.45 (s, 1H, OH), 7.30–7.22 (m, 3H, Te–Ph–H),
7.07 (s, 2H, Ar–H), 7.04 (s, 2H, Ar–H), 6.90 (s, 4H, Ar–H),
4.16 (d, 2H, J = 12.5 Hz, ArCH2Ar), 3.94–3.88 (m, 4H, OCH2),
3.83 (s, 4H, ArCH2Ar), 3.22 (d, 2H, J = 12.5 Hz, ArCH2Ar),
3.01 (t, 2H, J = 7.3 Hz, OCH2), 2.45 (t, 2H, J = 7.3 Hz, OCH2),
1.97–1.52 (m, 6H, CH2), 1.43 (s, 9H, t-Bu–H), 1.29 (s, 9H,
t-Bu–H), 1.11 (s, 18H, t-Bu–H), 1.03–0.92 (m, 6H, CH3). 13C
NMR: 154.37, 152.69, 150.10, 145.32, 143.90, 141.47, 138.49,
133.54, 133.28, 132.75, 129.16, 128.81, 128.38, 127.47, 125.93,
125.09, 124.59, 112.04, 72.55, 70.48, 38.75, 33.95, 31.73,
Acknowledgments
The Project partially sponsored by SRF for ROCS, SEM, the
Natural Science Foundation of Tianjin (08JCYBJC26700), the
National Natural Science Foundation of China (20604018) and
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