Synthesis and complexation of amphiphilic calix[4]arene phosphonates with organic molecules in solutions and Langmuir-Blodgett films

Article abstract of DOI:10.1016/j.molliq.2010.12.007

A family of amphiphilic alkoxycalix[4]arenes bearing phosphonyl groups directly attached to para positions of the aromatic rings is synthesized by the Arbuzov reaction of para-bromoalkoxycalix[4]arenes with alkyl esters of phosphorus (III) acid in the pre

Full text of DOI:10.1016/j.molliq.2010.12.007

Journal of Molecular Liquids 159 (2011) 117–123
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Synthesis and complexation of amphiphilic calix[4]arene phosphonates with organic
molecules in solutions and Langmuir-Blodgett films
A.V. Solovyov a, S.O. Cherenok a, O.I. Kalchenko a, L.I. Atamas a, Z.I. Kazantseva b, I.A. Koshets b,
I.F. Tsymbal a, V.I. Kalchenko a,
⁎
a
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska 5, 02660, Kyiv-94, Ukraine
Institute of Semiconductors Physics, National Academy of Sciences of Ukraine, Nauki 45, 02028, Kyiv-28, Ukraine
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 March 2010
Received in revised form 15 December 2010
Accepted 22 December 2010
Available online 5 January 2011
A family of amphiphilic alkoxycalix[4]arenes bearing phosphonyl groups directly attached to para positions of
the aromatic rings is synthesized by the Arbuzov reaction of para-bromoalkoxycalix[4]arenes with alkyl esters
of phosphorus (III) acid in the presence of NiBr2. Amphiphilicity of the calixarene phosphonates is controlled
by varying the quantities of the hydrophilic phosphoryl groups at the upper rim and the hydrophobic alkyl
groups at the lower rim. Complexation of the calixarenes with benzene derivatives and iso-butanol in
solutions is studied by RP HPLC and IR spectroscopy methods. Langmuir-Blodgett films of the calixarene
phosphonates are prepared. Physical characteristics and complexation of the films with volatile organic
molecules are characterized.
Keywords:
Calixarenes
Organophosphorus compounds
Supramolecular complexes
Langmuir-Blodgett films
Association constants
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
air have been investigated by the sensory system based on quartz
crystal microbalance technique.
Calixarenes are macrocyclic compounds of great interest in
supramolecular chemistry as bowl-shape platform for construction
of new molecules with remarkable host properties [1–5]. The ability to
form host-guest type complexes from a gas mixture [6], solutions [7,8],
crystalline state [9] and in the two-dimensional thin films [10–13]
have been reported. The calixarene thin films have been used to create
devices capable of recognizing cations, anions or neutral molecules in
solutions (artificial tongue) or in a gas mixture (artificial nose) [14,15].
A common method of the thin film formation is based on the
Langmuir-Blodgett technique (LB), using amphiphilic calixarenes
simultaneously possessing hydrophilic and hydrophobic groups at
the opposite rims of the macrocycle.
In this paper we describe the synthesis of a family of amphiphilic
calix[4]arenes possessing hydrophilic phosphoryl groups at the upper
rim and hydrophobic alkyl chains at the lower rim of the calixarene
core. The binding properties of the calixarene phosphonates with
benzene derivatives and iso-butanol in solutions have been studied.
The self-assembly of calixarene phosphonates at the water–air
interface, and LB film formation were investigated. Receptor proper-
ties of the calixarene LB films towards chloroform or acetone vapor in
2. Experimental
2.1. General
All reactions were carried out under nitrogen. Solvents were dried
and distilled by standard methods. 1H NMR spectra were recorded on
a Varian VXR instrument at 300 MHz. The 1H NMR data are referenced
to tetramethylsilane and 31P NMR data are referenced relative to
H3PO4 (85%) as the external standard. MS spectra were recorded on a
single-stage quadruple mass spectrometer using DCI technique. IR
spectra were recorded on M-80 spectrometer. CCl4 for spectroscopy
measurements was distilled over P2O5 and stored over molecular
sieves 3 Å to condition in which water absorption bands νa and νas in
this solvent (thickness of absorption layer 10 cm) were absent. The
melting points determined on a Boetius apparatus were uncorrected.
Analytical thin layer chromatography was performed on precoated
silica gel plates (Silufol). Silica gel (L 40/100) was used for column
chromatography.
Molecular modeling experiments of the phosphorylated calixarenes
were carried out using HyperChem 8.0 (PM3). (The evaluations copy is
free for download at http://www.hyper.com/Download/tabid/357/
Default.aspx). RMS gradient was equal to 0.01 kcal/A mol.
Bromocalixarenes 1-4 [16,17] and calixarene phosphonates 5a, 6b,
9a, 9b [18,19] were synthesized according the published procedures.
⁎
Corresponding author. Tel.: +380 445590667; fax: +380 445732643.
E-mail address: vik@ioch.kiev.ua (V.I. Kalchenko).
0167-7322/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2010.12.007

118
A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
2.2. Materials
Anal. Calcd. for C49H59O6P: C, 75.94; H, 7.67; P, 3.99 Found: C, 75.88; H,
7.75; P, 3.97.
2.2.1. General procedure for the preparation of calix[4]arene
phosphonates 5-9
2.2.6. 5,17-Bis(diethoxyphosphonyl)-25,27-dipropoxycalix[4]arene (6a)
Purification by column chromatography (CH2Cl2/acetone 5:1), Rf 0.6.
White solid: yield 70%; m.p. 160–163 °C; 1H NMR (CDCl3) 0.95 (t, 6 H, J
7.0 Hz, CH3CH2CH2O), 1.36 (t, 12 H, J 7.0 Hz, CH3CH2O), 1.86 (m, 4 H,
CH3CH2CH2O), 3.25 (d, 4 H, J 13.0 Hz, ArCH2eq), 3.70 (t, 8 H, J 7.0 Hz,
CH2O), 4.15 (m, 8 H, CH2OP), 4.47 (d, 4 H, J 13.0 Hz, ArCH2ax), 6.85 (t,
2 H, J 7.0 Hz, ArH-p), 7.05 (d, 4 H, J 7.0 Hz, ArH-m), 7.57 (d, 4 H, JPH
13.2 Hz, ArH), 9.00 (s, 2 H, OH); 31P δ 19.6; MS (CI) m/z 782 (M+, 100%).
M calculated 780.84. Anal. Calcd. for C42H54O10P2: P, 7.93 Found: P, 7.68.
To melted bromotetraheptyloxy(octyloxy)calix[4]arenes 1b,c and
4 b,c (0.01 mmol) or to solutions of bromotetrapropoxycalix[4]arenes
2 and 3 (0.01 mmol) in benzonitrile (10 mL) in the presence of NiBr2
(0.002 mmol for each bromine atom of the calix[4]arene), the
phosphites (0.12, 0.24, 0.48 mmol accordingly) were added dropwise
at 170 °C. The resulting solutions were kept at the temperature for 1 h.
The reaction mixture was evaporated in vacuum (0.05 mm, 100 °C)
resulting in an oil. The oil was then dissolved in methylene chloride,
and that the solution was washed with NH4OH, water and
subsequently dried over Na2SO4. The solution was evaporated to
dryness and a residue was purified by column chromatography. Yields
were calculated to be 40–70%.
2.2.7. 5,17-Bis(diethoxyphosphonyl)-25,26,27,
28-tetrapropoxycalix[4]arene (7a)
Purification by column chromatography (CH2Cl2/acetone 5:1), Rf
0.6. White solid: yield 70%; m.p. 159–162 °C; 1H NMR (CDCl3) 0.90 (t,
6 H, J 7.0 Hz, CH3CH2CH2O), 1.10 (t, 6 H, J 7.0 Hz, CH3CH2CH2O), 1.37
(t, 12 H, J 7.0 Hz, CH3CH2O), 1.90 (m, 8 H, CH3CH2CH2O), 3.22 (d, 4 H, J
13.0 Hz, ArCH2eq), 3.69 (t, 4 H, J 7.0 Hz, CH2O), 4.18 (m, 12 H, CH2O+
CH2OP), 4.46 (d, 4 H, J 13.0 Hz, ArCH2ax), 6.10 (d, 4 H, J 7.2 Hz, ArH-m),
6.23 (t, 2 H, J 7.2 Hz, ArH-p), 7.56 (d, 4 H, JPH 13.2 Hz, ArH-m); 31P
NMR δ 20.1; MS (CI) m/z 866 (M+, 100%). M calculated 865.01. Anal.
Calcd. for C48H66O10P2: P, 7.16 Found: P, 7.08.
2.2.2. 5-Dibutyloxyphosphonyl-25,26,27,28-tetrapropoxycalix[4]arene
(5b)
Purification by column chromatography (CH2Cl2/acetone 10:1), Rf
0.5. Oil: yield 50%; 1H NMR (CDCl3) δ 0.92 (t, 6 H, J 7.2 Hz,
CH3CH2CH2CH2O), 0.97, 1.07 (two t, 6 H+6 H, J 7.5 Hz, CH3CH2CH3O),
1.36 (m, 4 H, CH3CH2CH2CH2O), 1.60 (m, 4 H, CH3CH2CH2CH2O), 1.92
(m, 8 H, CH3CH2CH2O), 3.15, 3.19 (two d, 2 H+2 H, J 13.2 Hz,
ArCH2eq), 3.89 (m, 12 H, CH2O), 4.44, 4.46 (two d, 2 H+2 H, J
13.2 Hz, ArCH2ax), 6.50 (m, 6 H, ArH-m+ArH-p), 6.62 (t, 1 H, J 7.0 Hz,
ArH-p), 6.70 (d, 2 H, J 7.0 Hz, ArH-m), 7.18 (d, 2 H, JPH 13 Hz, ArH-m);
31P NMR δ 20.6; MS (CI) m/z 786 (M+, 100%). M calculated 783.975.
Anal. Calcd. for C48H65O7P: C, 73.44; H, 8.35; P, 3.95 Found: C, 73.21; H,
8.33; P, 3.85.
2.2.8. 5,17-Bis(diphenylphosphonyl)-25,26,27,
28-tetrapropoxycalix[4]arene (7b)
Purification by column chromatography (CH2Cl2/CH3OH/acetone
30:1:1), Rf 0.3. White solid: yield 50%; m.p. 107–109 °C; 1H NMR (CDCl3)
0.91 (t, 6 H, J 7.0 Hz, CH3CH2CH2O), 1.08 (t, 6 H, J 7.0 Hz, CH3CH2CH2O),
1.83 (m, 4 H, CH2), 1.98 (m, 4 H, CH2), 3.14 (d, 4 H, J 13.0 Hz, ArCH2eq),
3.62 (t, 4 H, J 7.0 Hz, CH2O), 4.11 (t, 4 H, J 7.0 Hz, CH2O), 4.44 (d, 4 H, J
13.0 Hz, ArCH2ax), 6.04 (d, 4 H, J 7.2 Hz, ArH-m), 6.26 (t, 2 H, J 7.2 Hz,
ArH-p), 7.42 (d, 4 H, JPH 13.2 Hz, ArH-m), 7.55 (m, 12 H, meta+para
protons of C6H5 groups), 7.73, 7.76 (two d, 4 H+4 H, JPH 13 Hz,
diastereotopic ortho protons of C6H5 group); 31P NMR δ 30.5. Anal. Calcd.
for C64H66O6P2: P, 6.2. Found: P, 6.16.
2.2.3. 5-Diethoxyphosphonyl-25,26,27,28-tetraheptyloxycalix[4]arene
(5c)
Purification by column chromatography (CH2Cl2/CH3OH 20:1), Rf
0.5. Oil: yield 65%; 1H NMR (CDCl3) 0.93 (m, 12 H, CH3(CH2)6O), 1.27
(t, 6 H, J 7.2 Hz, CH3CH2O), 1.34, 1.40 (two m, 32 H, CH2), 1.95 (m, 8 H,
CH2CH2O), 3.17, 3.21 (two d, 2 H+2 H, J 13.2 Hz, ArCH2eq), 3.91
(m, 12 H, CH2O), 4.45, 4.48 (two d, 2 H+2 H, J 13.2 Hz, ArCH2ax), 6.59
(m, 9 H, ArH), 7.17 (d, 2 H, JPH 13 Hz, ArH-m); 31P NMR δ 20.1; MS (CI)
m/z 954 (M+, 100%). M calculated 953.35. Anal. Calcd. for C60H89O7P:
P, 3.25 Found: P, 3.12.
2.2.9. 5-Bromo-11,17,23-tris(diethoxyphosphonyl)-25,26,27,
28-tetraheptyl-oxycalix[4]arene (8a)
Purification by column chromatography (CH2Cl2/CH3OH 3:1), Rf
0.4. Oil: yield 25%; 1H NMR (CDCl3) 0.92 (m, 12 H, CH3(CH2)5CH2O),
1.10 (t, 6 H, J 7.0, CH3CH2O), 1.33 (m, 12 H+24 H, CH3CH2O+CH3
(CH2)4CH2CH2O), 1.96 (m, 8 H, CH3(CH2)4CH2CH2O), 3.30, 3.33 (two
d, 2 H+2 H, J 13.0 Hz, CH2eq), 3.71 (m, 8 H, CH3(CH2)4CH2CH2O), 4.13
(t, 12 H, J 7.0 Hz, CH3CH2O), 4.46, 4.49 (two d, 2 H+2 H, J 13.0 Hz,
ArCH2ax), 6.53 (s, 2 H, ArH-m), 6.91 (d, 2 H, JPH 13.2 Hz , ArH-m), 7.55,
7.57 (two d, 4 H, JPH 13.2 Hz, C6H2); 31P NMR δ 19.5. Anal. Calcd. for
2.2.4. 5-Diethoxyphosphonyl-25,26,27,28-tetraoctyloxycalix[4]arene
(5d)
Purification by column chromatography (CH2Cl2/acetone 20:1), Rf
0.6. Oil: yield 60%; 1H NMR (CDCl3) 0.93 (m, 12 H, CH3(CH2)7O), 1.28
(t, 6 H, J 7.2 Hz, CH3CH2O), 1.34, 1.40 (two m, 40 H, CH2), 1.94 (m, 8 H,
CH2CH2O), 3.18, 3.22 (two d, 2 H+2 H, J 13.2 Hz, ArCH2eq), 3.92
(m, 12 H, CH2O), 4.46, 4.49 (two d, 2 H+2 H, J 13.2 Hz, ArCH2ax), 6.60
(m, 9 H, ArH), 7.19 (d, 2 H, JPH 13 Hz, ArH-m); 31P NMR δ 20.75; MS
(CI) m/z 1010 (M+, 100%). M calculated 1009.45. Anal. Calcd. for
C68H106BrO13P3: C, 62.61 H, 8.19 P, 7.12 Found: C, 62.58 H, 8.23 P, 7.06.
2.2.10. 5-Bromo-11,17,23-tris(diethoxyphosphonyl)-25,26,27,
28-tetraoctyl-oxycalix[4]arene (8b)
C64H97O7P: P, 3.07 Found: P, 2.96.
Purification by column chromatography (CH2Cl2/CH3OH 25:1), Rf.
0.5. Oil: yield 30%; 1H NMR (CDCl3) 0.93 (m, 12 H, CH3(CH2)6CH2O),
1.12 (t, 6 H, J 7.0 Hz, CH3CH2O), 1.34 (m, 12 H+30 H, CH3CH2O+CH3
(CH2)5CH2CH2O), 1.98 (m, 8 H, CH3(CH2)5CH2CH2O), 3.35, 3.38 (two d,
2 H+2 H, ArCH2eq), 3.80 (m, 8 H, CH3(CH2)5CH2CH2O), 4.20 (t, 12 H, J
7.0 Hz, CH3CH2O), 4.47, 4.49 (two d, 2 H+2 H, ArCH2ax), 6.61 (s, 2 H,
ArH-m), 7.00 (d, 2 H, JPH 13.2 Hz, ArH), 7.58, 7.61 (two d, 2 H+2 H, JPH
13.2 Hz, ArH); 31P NMR δ 19.7. Anal. Calcd. for C72H114BrO13P3: C,
64.25 H, 9.17 P, 6.28 Found: C, 62.31 H, 9.12 P, 7.14.
2.2.5. 5-Phenylisopropoxyphosphonyl-25,26,27,
28-tetrapropoxycalix[4]arene (5e)
Purification by column chromatography (CH2Cl2/acetone 5:1), Rf
0.4. White solid: yield 50%; m.p. 55–58 °C; 1H NMR (CDCl3) δ 1.02 (m,
12 H, CH3), 1.27, 1.29 (two d, 3 H+3 H, J 7.5 Hz, diastereotopic
CH3CH), 1.93 (m, 8 H, CH2CH2O), 3.17, 3.21 (two d, 2 H+2 H, J
13.5 Hz, ArCH2eq), 3.85 (m, 8 H, CH2O), 4.45 (d, 4 H, J 13.5 Hz,
ArCH2ax), 4.55 (m, 1 H, CH3CH), 6.51 (m, 7 H, ArH-m+ArH-p), 6.72
(d, 2 H, J 7.0 Hz, ArH-m), 7.17, 7.35 (two d, 1 H+1 H, JPH 13 Hz,
diastereotopic ArH-m), 7.43 (m, 2 H, meta protons of C6H5 group),
7.51 (m, 1 H, para proton of C6H5 group), 7.69, 7.71 (two d, 1 H+1 H, J
PH 13 Hz, diastereotopic ortho protons of C6H5 group); 31P NMR δ 31.6;
2.2.11. 5,11,17,23-Tetrakis(diethoxyphosphonyl)-25,26,27,
28-tetraheptyloxy-calix[4]arene (9c)
Purification by column chromatography (CH2Cl2/CH3OH 3:1), Rf
0.2. White solid: yield 60%; m.p. 110–112 °C; 1H NMR (CDCl3) 0.91

A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
119
(t, 12 H, J 7.5 Hz, CH3(CH2)6O), 1.21 (t, 24 H, J 7.5 Hz, CH3CH2O), 1.32,
1.38 (two m, 32 H, CH3(CH2)5CH2O), 1.95 (m, 8 H, CH3(CH2)5CH2O),
3.32 (d, 4 H, J 13.0 Hz, ArCH2eq), 3.96 (m, 24 H, CH2OP), 4.48 (d, 4 H, J
13.0 Hz, ArCH2ax), 7.27 (d, 8 H, JPH 13 Hz , ArH-m); 31P NMR δ 19.9.
Anal. Calcd. for C72H116O16P4: P, 9.10 Found: P, 8.76.
prepared by dissolving 9a in an acetonitrile–water (86:14, v/v) mixture to
give the calixarene concentrations 0.76, ×10−3 M, 1.45×10−3 M,
2.15×10−3M and 3.05×10−3M. The analytes for injections were
dissolved in the same acetonitrile–water (86:14, v/v) mixture
(C=0.3×10−4). The amount of the sample injected was 20 μL. Each of
the samples was analyzed five times. All chromatograms were obtained at
22 °C. The flow rate was 0.5 mL/min, and the UV detector was operated at
254 nm. The dead time (t0) was measured with NaNO2. The mobile phase
which contained the calixarene as additive was equilibrated for 10 h
before analysis. Under these conditions the column was saturated with
the calixarene additive.
2.2.12. 5,11,17,23-Tetrakis(diethoxyphosphonyl)-25,26,27,
28-tetraoctyloxy- calix[4]arene (9d)
Purification by column chromatography (CH2Cl2/CH3OH 25:1),
Rf 0.2. White solid: yield 55%; m.p. 95–97 °C; 1H NMR (CDCl3) 0.92
(m, 12 H, CH3(CH2)6CH2O), 1.23 (t, 24 H, J 7.5 Hz, CH3CH2O), 1.33,
1.40 (two m, 40 H, CH3(CH2)6CH2O), 1.98 (m, 8 H, CH3(CH2)6CH2O),
3.33 (d, 4 H, J 13.0 Hz, ArCH2eq), 3.98 (m, 24 H, CH2OP), 4.49 (d, 4 H, J
13.0 Hz, ArCH2ax), 7.28 (d, 8 H, JPH 13 Hz, ArH-m); 31P NMR δ 19.3; MS
(CI) m/z 1418 (M+, 100%). M calculated 1417.73. Anal. Calcd. for
2.3.2. Langmuir-Blodgett films formation and investigation
The behavior of the calixarene molecules on a water surface has
been investigated by π–A Langmuir isotherm experiments with R&K
(Wiesbaden, Germany) equipment for LB film preparation [11].
Surface tension was registered by the Wilhelmy method. Chloroform
solutions of the calixarenes (C=0.5 mg/ml) were used for the
monolayer formation on the bi-distilled water sub-phase. The
hydrophobized silicon wafer (for ellipsometry measurements) and
quartz crystal resonators with hydrophilic surface (for investigation of
receptor properties) were used as substrates. The silicon wafer was
hydrophobized by treatment with boiling HCl:H2O2:H2O mixture and
then exposed with the hexamethyldisilazan vapor during 30 min.
Newly Ag (or Ni) deposited quartz surface possesses hydrophilic
features and does not require any treatment.
Receptor properties of the phosphonylcalixarene molecules
towards organic volatiles were studied by Quartz Crystal Microbal-
ance (QCM) technique. QCM technique uses the proportionality
between a mass loaded onto quartz surface and an oscillations
frequency shift as a basis [22]. By measuring the frequency shift, one
can easily investigate an adsorption-desorption processes occurring
onto the sensor's surface. Sensitivity of this method is a quite high —
about 1 ng/Hz, which allows for the detection of very low concentra-
tion of organic vapors. The 8-channel QCM array with all necessary
equipment (gas cell, gas-supplying system and electronic circuits,
etc.) has been designed in the Institute of Semiconductor Physics NAS
of Ukraine. Experiment control and data acquisition were implemen-
ted with PC by means of domestic software. The gas-supplying regime
chosen for the experiment was non-flow type — after rapidly injecting
the analyte the gas cell cuts off from the pipeline and no gas flow
occurs during measuring period. Detailed description of device and
gas supplying regime can be found in [23].
C76H124O16P4: P, 8.74 Found: P, 8.56.
2.3. Methods
2.3.1. RP HPLC
The association constants of the complexes of calixarene tetrapho-
sphonate 9a with a series of benzene derivatives (Table 1) were
determined by the RP HPLC method using analysis of the linear
dependence of a capacity factor of the aromatic guest versus the
calixarene concentration in a mobile phase. The association constants
KA were calculated according the published procedure [20,21] using
Eq. (1)
ꢀ
ꢁ
′
′
′
k0 1= k −1= k0
½CAꢀ
KA
=
ð1Þ
where k’o and k’ are capacity factors in the absence and the presence of
the calixarene additive in the mobile phase respectively; [CA] is the
calixarene concentration in the mobile phase.
The liquid chromatographic system consisted of a high-pressure
pump HPP 4001 (Laboratorni Pristroje, Praha) connected to a Rheodyne
sample 7120 injector with a 20 μL loop (Rheodyne, Berkeley) and an
ultraviolet–visible (UV–VIS) detector LCD 2563 (Laboratorni Pristroje,
Praha). The column (150×3.3 mm i.d.) was packed with Separon SGX
C18 (5 μm) (Lachema). Acetonitrile–water (86:14, v/v) mixture was used
as a blank mobile phase. The calixarene contained mobile phases were
3. Results and discussion
Table 1
The association constants of the host-guest complexes of calixarene 9a in acetonitrile–
water (86:14, v/v) solution.
3.1. Synthesis and stereochemistry
No Guest
KA, M−1 No Guest
(RSD, %)
KA, M−1
(RSD, %)
Several methods of the calixarene upper rim phosphorylation
have been described [24]. The most convenient of these employs
the nickel catalyzed Arbuzov reaction of the easily accessible para-
bromoalkoxycalixarenes [18,19,25–29]. Dialkoxy- and tetraalkoxyca-
lix[4]arenes 5-9 containing one, two, three or four hydrophilic
phosphoryl groups have been synthesized by the reaction of
bromocalixarenes 1-4 with alkyl esters of phosphorus (III) acid in
the presence of a catalytic amount of NiBr2 at 170 °C in benzonitrile
solution (Scheme 1). (Phosphorylation of the low melting tetra-
heptyloxy(octyloxy)bromocalix[4]arenes 1b,c and 4 b,c was per-
formed without solvent). The yields of phosphorylated calix[4]arenes
5-7 and 9 were in the range of 40–70%. In case of tetrabromocalix[4]
arenes 4b,c the triphosphorylated calixarenes 8a,b were also isolated
with 25 or 30% yields respectively.
1
2
3
4
5
6
7
8
9
Trichloromethylbenzene 13 (17) 20 o-Fluorophenol
105 (13)
107 (5)
114 (7)
130 (17)
p-Chloroaniline
o-Dibromobenzene
Hexafluorobenzene
p-Bromophenol
p-Chlorophenol
Benzene
14 (16) 21 Dimethyl-p-toluidine
15 (6) 22 Chlorobenzene
23 (15) 23 Guaiacol
29 (25) 24 Trifluoromethylbenzene 142 (18)
31 (18) 25 p-Fluorophenol
32 (8) 26 Toluene
32 (12) 27 o-Phenylenediamine
39 (2) 28 m-Dinitrobenzene
44 (16) 29 m-Toluidine
49 (12) 30 p-Bromotoluene
61 (10) 31 Anisaldehyde
65 (13) 32 Veratrole
146 (9)
152 (4)
178 (8)
197 (4)
201 (7)
217 (5)
224 (4)
263 (3)
268 (6)
294 (5)
311 (3)
328 (3)
329 (8)
Phenol
m-Nitrophenol
10 p-Xylene
11 iso-Propylbenzene
12 Benzyl alcohol
13 Benzaldehyde
14 Iodobenzene
70 (7)
71 (9)
33 o-Bromotoluene
34 m-Xylene
15 p-Toluidine
In accordance with the NMR data, the macrocyclic skeleton of
calixarenes 5-9 exists in the cone shaped conformation. This is
confirmed by the presence of two doublets of the AB spin system for
axial and equatorial protons of the methylene bridges in the 1H NMR
16 p-Methoxytoluene
17 Veratraldehyde
18 N,N-Dimethylaniline
19 Salicyl aldehyde
84 (16) 35 p-Cyanophenol
86 (8)
93 (3)
94 (17)
36 Aniline
37 p-Aminophenol

120
A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
Scheme 1.
spectra, and the presence of only one signal in the 31P NMR spectra.
Coupling constants of the axial and equatorial protons are 13 Hz, the
difference of their chemical shifts Δδ is in the range 0.8–1.2 ppm. The
parameter Δδ≈0.8 ppm for dialkoxycalixarenes 6 confirms the
stereochemically rigid flattened cone (C2v symmetry) conformation
(Fig. 1a) [30]. In this conformation phosphorylated benzene rings are
forced to the coplanar orientation due to formation of the intramo-
lecular hydrogen bonds OH…OPr at the macrocyclic lower rim. For
tetraalkoxycalixarenes 5, 7-9 the parameter Δδ≈1.2 ppm indicates
the regular cone (C4v symmetry) conformation (Fig. 1b) [31].
3.2. Investigation of the complexation by IR spectroscopy
In contrast to the well-documented complexation of phosphory-
lated calixarenes with metal cations, their complexation with organic
molecules is less investigated [25]. The presence of the rather basic
P=O moieties reveals the calixarenes as receptors of organic
molecules possessing CH, NH, OH protonodonor groups. Binding of
iso-butanol or phenol H-donor molecules with mono-, di-, and
tetraphosphorylated calix[4]arenes 5a, 6b, 9a was investigated by
the IR spectroscopy in CCl4 solutions. Calixarenes 5a, 6b, 9a possess

A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
121
Fig. 1. Energy minimized structures of dipropoxycalixarene diphosphonate 6b (a), tetrapropoxycalixarene tetraphosphonate 9a (b) and the host-guest inclusion complexes of 9a
with toluene (c) and aniline (d) molecules (HyperChem 8.0, PM3).
two types of proton acceptor centers: oxygen atoms at the lower rim
of the macrocycle and oxygen atoms of P=O groups at the upper rim.
As shown by the model experiment with the upper rim unsubstituted
tetrapropoxycalixarene 10, the proton acceptor ability of the ether
oxygens at the lower rim is not significant.
where [Ccalix], [Cguest], [Ccomplex] are the equilibrium concentrations of
the calixarene host, the iso-butanol or phenol guest molecules and
their host–guest complex respectively determined by the IR spec-
troscopy method from adsorption intensity of the guest's free and the
guest's associated OH groups.
Enthalpy ΔH of the complexation was calculated using Eq. (3)
−ΔH = R tg a
ð3Þ
O
where the tg α parameter was determined from a linear dependence
of lnKa vs 1/T.
O
O
O
Pr
Pr
Pr
Pr
So, the association constant Ka and enthalpy ΔH for complexation
of monophosphonylcalixarene 5a with iso-butanol are 15.8 L mol−1
and 2.4 kcal mol−1, respectively. Phenol forms a more stable complex
with calixarene 5a (Ka =2200 L mol−1 and ΔH=6.5 kcal mol−1).
10
In the IR spectra of the mixtures 10 (1·10−2 M) with iso-butanol
(5·10−5 M) or with phenol (5·10−5 M) in CCl4 solutions no shift of
the absorption band of the hydroxyl groups induced by hydrogen
bonding was observed. However, IR spectra of mixtures of phosphor-
ylated calixarenes 5a, 6b, 9a (1·10−2–1·10−3 M) with iso-butanol or
phenol (1·10−2–5·10−3 M) reveal the presence of the strong
hydrogen bonds. The Δν (OH) values for butanol and phenol consist
of 220 cm−1 and 390 cm−1 respectively. The optical density of the
hydroxyl absorption bands increases along with the number of
phosphoryl groups in calixarenes 5ab6bb9a.
The absorption band shifts of P=O groups in calixarenes 5a, 6b
induced by the hydrogen bonding with iso-butanol or phenol
molecules are 29 cm−1 and 37 cm−1 respectively.
The association constant Ka for complexation of monophosphonyl-
calixarene 5a with iso-butanol and phenol molecules were calculated
according to Eq. (2)
3.3. Investigation of the complexation by RP HPLC and molecular
modeling methods
The stability constants of calixarene complexes with neutral
organic molecules in solutions are usually determined by NMR
spectroscopy [31] or microcalorimetry [19] methods. Nevertheless,
it has been documented [20,21,32,33] that under reversed-phase
liquid chromatography conditions the addition of a calixarene to a
mobile phase leads to decreasing sorption of organic solutes on a
sorbent surface due to formation of the host-guest inclusion
complexes of the calixarene host with the organic guest. Stability
constants of the 1:1 complexes can be determined from a linear
dependence between the guest capacity factors and the calixarene
concentration in the mobile phase (see Experimental).
h
i
Ccomplex
The association constants KA of the complexes of calixarene 9a
with a series of benzene derivatives determined by the RP HPLC
method in acetonitrile–water (86:14, v/v) solution as the mobile
h
i
Ka
=
ð2Þ
½Ccalix
ꢀ
Cguest
⋅

122
A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
phase are presented in (Table 1). The constants are in the range of 13–
329 M−1. Their values depend upon electronic nature, size, quantity
and geometrical position (ortho, meta, para) of substituents at
benzene ring of the guest molecules.
a
0
-50
100ppm
500ppm
1000ppm
The lowest KA value (13 M−1) was estimated for the calixarene 9a
complex with trichloromethylbenzene. The trifluoromethylbenzene–
9a complex was determined to be almost 10-fold more stable (KA
142 M−1). The toluene–9a complex has KA 152 M−1 which is larger
than for benzene complex (KA 32 M−1). Two methyl groups in meta-
2000ppm
-100
-150
-200
-250
position of the benzene ring increase KA of meta-xylene to 294 M−1
.
4000ppm
Substitution of benzene ring in para-position with methyl or methoxyl
groups leads to the decreasing KA to 44 M−1 (para-xylene) and 84 M−1
(para-methoxytoluene). The replacement of the bromine atom in
ortho-dibromobenzene (KA =15 M−1) by the methyl group increases
KA to 268 M−1 (ortho-bromotoluene). The largest values of the
association constants are reported for the calixarene complexes with
para-cyanophenol (311 M−1) and para-aminophenol (329 M−1).
The observed relationship between the nature of the guest molecule
and KA values reflects the complicated character of the complexation
process.
The mode of the host-guest complexation is illustrated by the
molecular modeling calculations (Fig. 1c,d). As it is shown, the toluene
molecule is included into the calixarene 9a cavity by methylene group
forming CH–π bonds with aromatic rings of the macrocyclic skeleton.
In the inclusion complex with the aniline molecule its NH2 group is
oriented outside the calixarene cavity.
CHCl3
6000ppm
800
0
200
400
600
time, sec
b
10
5
0
100ppm
500ppm
1000ppm
-5
-10
-15
-20
-25
-30
-35
2000ppm
4000ppm
3.4. The calixarene Langmuir-Blodgett films and their receptor properties
6000ppm
The π–A (π — the pressure inside the film, A — the area per one
molecule) Langmuir isotherm experiments with amphiphilic calixarenes
5a,e and 9a on a water surface confirm the Langmuir monolayer
formation (Fig. 2 ). The area per molecule (A) for closely packed layers
are 1.75 0.05 nm2 (5a), 1.30 0.05 nm2 (5e) and 2.07 0.05 nm2 (9a)
that corresponds with our previous experiments on the similar calix[4]
arenes [11].
The Langmuir-Blodgett films of calixarenes 5a,e and 9a have been
prepared and investigated as well. The calixarene LB films were
formed on the polished silicon plates coated with a native oxide by
immersing the plates using vertical transfer procedure. The LB films
are formed at π 18–20 mN/m and dipping speed 2 mm/min. The LB
film thicknesses of 5a,e and 9a on the silicon substrates as measured
by the optical ellipsometry method are 1.0 0.1 nm.
CH3-CO-CH3
10000ppm
800 1000
0
200
400
600
time,sec
Fig. 3. Kinetic responses of the QCM sensors covered with calixarene 5a (30
monolayers) to sorption of chloroform (a) and acetone (b) at different concentrations
in air.
The kinetic responses of 5a coated sensors to different concentra-
tions (100–10,000 ppm) of acetone and chloroform in air are
presented in Fig. 3. The sensor has a quick kinetic response (less
than a second), high reversibility and reproducibility.
The stoichiometry of the analyte–calixarene (S) in the LB films has
been estimated using the QCM sensor responses to chloroform and
acetone at concentrations close to their saturated vapor pressure [34].
Taking into account linearity of Sauerbrey equation [22] the
stoichiometry S can be calculated from expression (4)
In order to investigate the calixarenes 5a,e and 9a receptor
features their multilayered films (25–30 monolayers) were formed on
the quartz resonator surfaces of the QCM-based sensory systems [23].
60
50
40
M
calix = Manal
S =
ð4Þ
Δfcalix = Δfanal
Table 2
30
Responses of the QCM sensors on the calixarene LB films deposition (Δfcalix), the
analytes sorption (Δfanal) and stoichiometry of analyte–calixarene (S).
II
20
Sensor
parameters
Chloroform
5a
Acetone
5a
5e
9a
5e
9a
I
10
0
7000a
850
2056
180
11.4
13
4646
250
4600a
120
III
Δfcalix, Hz
Δfanal, Hz
2056
850
2.4
4646
1750
Δfcalix/Δfanal
2.6
6.6
2.5
8.2
10.6
1.3
17.2
13.3
0.8
38.3
21.5
0.6
M
S
calix/Manal
6.4
2.7
0
1.0
2.0
3.0
Area per molecule, nm2/molecule
1.1
a
The quartz sensors with different number of the calixarene 9a LB monolayers onto
their surfaces were used for the chloroform and acetone experiments.
Fig. 2. π–A Langmuir isotherms of monolayers of compounds 5a (I), 9a (II), and 5e (III).

A.V. Solovyov et al. / Journal of Molecular Liquids 159 (2011) 117–123
123
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where Δfcalix and Δfanal are frequency shift caused by the calixarene LB
films deposition and the analyte molecules sorption onto the sensor
surface. Mcalix and Manal are molecular weights of the calixarene and
analyte respectively.
The S data obtained from Eq. (4) are presented in Table 2. The
stoichiometry of chloroform–calixarene equals to 1.3 for 9a, 2.5 for 5e
and 2.7 for 5a. The stoichiometry of acetone–calixarene is 0.6, 0.8 and
1.1 for 9a, 5e and 5a respectively.
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4. Conclusion
The amphiphilic calix[4]arene phosphonates easily synthesized by
the Arbuzov reaction of the para-bromoalkoxycalixarenes form the
host-guest inclusion complexes with different organic molecules in
solution. The calixarene Langmuir-Blodgett films layered onto QCM
chemosensor surface can reversibly adsorb vapors of volatile organic
compounds in air.
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