Investigation of hydrogen bonding in p-sulfonatocalix[4]arene and its thermal stability by vibrational spectroscopy

Article abstract of DOI:10.1016/j.molstruc.2019.06.008

The vibrational spectra of p-sulfonatocalix [4] arene were studied. The geometrical parameters, the energies, the frequencies and the intensities of the bands in the IR and Raman spectra are calculated for four conformations. The most stable conformation of the p-sulfonatocalix[4]arene is the cone due to the cooperative cyclic intramolecular hydrogen bonding system. The strength of the hydrogen bonds depends on the type of substituent on the upper rim of the calixarene molecules. We studied the process of destruction of calixarenes using IR spectroscopy and TGA methods. Characteristic bands for each conformation were selected. HOMO covers aromatic units with notable conjugation, and LUMO belongs to sulfonate groups.

Full text of DOI:10.1016/j.molstruc.2019.06.008

Accepted Manuscript
Investigation of hydrogen bonding in p-sulfonatocalix[4]arene and its thermal stability
by vibrational spectroscopy
V.L. Furer, A.E. Vandyukov, A.R. Khamatgalimov, S.R. Kleshnina, S.E. Solovieva,
I.S. Antipin, V.I. Kovalenko
PII:
S0022-2860(19)30721-5
DOI:
https://doi.org/10.1016/j.molstruc.2019.06.008
MOLSTR 26650
Reference:
To appear in: Journal of Molecular Structure
Received Date: 4 February 2019
Revised Date: 29 May 2019
Accepted Date: 3 June 2019
Please cite this article as: V.L. Furer, A.E. Vandyukov, A.R. Khamatgalimov, S.R. Kleshnina, S.E.
Solovieva, I.S. Antipin, V.I. Kovalenko, Investigation of hydrogen bonding in p-sulfonatocalix[4]arene
and its thermal stability by vibrational spectroscopy, Journal of Molecular Structure (2019), doi: https://
doi.org/10.1016/j.molstruc.2019.06.008.
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ACCEPTED MANUSCRIPT
TGA heating curves of samples of p-sulfonatocalix[4]arene (SC4) and p-tertbutylcalix[4]arene
(TB4) molecules from room temperature to 600° C. The inset images show the three IR spectra
of the gas phase released during a) 220 ° C, (b) 290 ° C, (c) 400 ° C.

ACCEPTED MANUSCRIPT
Investigation of hydrogen bonding in p-sulfonatocalix[4]arene and its thermal
stability by vibrational spectroscopy
a*
b
b,d
b
b,c
V.L. Furer , A.E. Vandyukov , A.R. Khamatgalimov , S.R. Kleshnina , S.E. Solovieva , I.S.
b,c
b,d
Antipin , V.I. Kovalenko *
a
Kazan State Architect and Civil Engineering University, 1 Zelenaya Str., 420043 Kazan, Russia
b
A.E. Arbuzov Institute of Organic and Physical Chemistry, RAS, 8 Arbuzov Str., 420088 Kazan, Russia
c
Kazan Federal University, Kremlyovskaya Str., 420008, Kazan, Russia
d
Kazan National Research Technological University, 68, Karl Marx Str., Kazan 420015, Russia
Abstract
The vibrational spectra of p-sulfonatocalix [4] arene were studied. The geometrical parameters,
the energies, the frequencies and the intensities of the bands in the IR and Raman spectra are calculated
for four conformations. The most stable conformation of the p-sulfonatocalix[4]arene is the cone due to
the cooperative cyclic intramolecular hydrogen bonding system. The strength of the hydrogen bonds
depends on the type of substituent on the upper rim of the calixarene molecules. We studied the process
of destruction of calixarenes using IR spectroscopy and TGA methods. Characteristic bands for each
conformation were selected. HOMO covers aromatic units with notable conjugation, and LUMO
belongs to sulfonate groups.
Keywords: Calixarenes, IR spectra, Raman spectra, Hydrogen bonding, DFT
*
Tel.: +7-843-5104737; fax.: +7-843-2387972. E-mail address: furer@kgasu.ru (V.L. Furer).
*
Tel.: +7-843-2732283; fax.: +7-843-2732253. E-mail address: koval@iopc.ru (V.I. Kovalenko).

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2
1. Introduction
Calixarenes are macrocyclic compounds characterized by the presence of a cavity and capable of
forming supramolecular complexes [1-6]. For biological experiments and drugs, solubility in water is
particularly important. It is obtained by attaching charged functional groups to calixarenes [1-6].
Calixarenes with sulfonate groups on the upper rim are soluble in water and play a special role in the
interaction with biological objects [7-9]. They interact with cells, are used as bacteria sensors and for
drug delivery [7-9]. Calixarene sulfonates are biocompatible and non-toxic [10]. The ability of
calixarenes to bind metals is used in ecology [11]. Therefore, studying the structure of calixarenes with
sulfonate groups is an important task. The IR spectra of calixarenes have been studied [12-25].
However, as a general rule, IR spectroscopy is used for analytical purposes, and only the stretching
vibrations of the hydroxyl groups are taken into account [11]. Raman spectra of calixarenes are very
rarely studied [13].
The thermogravimetric analysis (TGA) method is used to study processes accompanied by
changes in the mass of the analyte, usually with changes in temperature. This method is extremely useful
for studying objects containing, in addition to the main substance, various compounds - crystalline
hydrates, solvates, clathrates. This method is of interest for the study of thermal decomposition
processes of substances, composites, and materials. Unfortunately, the TGA method is still very rarely
used to study the thermal stability of calixarenes.
In this work, we studied changes in IR spectra during the heating process of p-
sulfonatocalix[4]arene and p-tert-butylcalix[4]arene. It is important to determine how bands of polar
sulfonate groups appear in vibrational spectra of calixarenes and their modification in the
conformational transformation process. The DFT method was used to interpret the IR and Raman
spectra of p-sulfonatocalix[4]arene. We identified bands of sulfonate groups and established how these
groups affect the thermal stability of calixarenes.
2
. Experimental
The p-sulfonatocalix[4]arene (SC4) was produced according to a known method (Fig. 1) [26].
Calix[4]arene with tert-butyl substituents (TB4) was also prepared and studied (Fig. 1).

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IR spectra of crystalline samples of calixarenes were recorded in KBr tablets in the range of
-1
-1
4
000-400 cm with a resolution of 4 cm using a Bruker Vector 22 spectrophotometer. Sixty-four
-1
accumulated scans for each spectrum. The Raman spectra were recorded in the 3500-100 cm region via
a Bruker FT-Raman RAM II module of the FTIR Vertex 70 spectrometer. The 1064 nm excitation line
of the Nd: YAG laser with a power of 50 mW was used.
TGA measurements were performed on the NETZSCH STA 449C Jupiter device (Germany) in
an argon atmosphere in a temperature range of + 30 ° C to + 600 ° C. The heating rate was 10 deg/min.
The samples were placed in unsealed aluminum crucibles (to remove released products and reduce the
effect of overpressure).
3
. Computational procedure
As a first approximation to optimize the geometry of p-sulfonatocalix[4]arene, we used
experimental data obtained by X-ray diffraction [27]. Optimization was performed using the B3LYP
density functional [28,29], 6-31G(d,p) basis set [30] and the Gaussian-09 program [31]. Calculated
frequencies were scaled using the equation νobs = (1.0087 - 0.0000163νcal)νcal [32].
The relative intensities of the Raman spectrum lines were calculated from the Raman activity Si
obtained using the Gaussian-09 program, according to the following equation:
4
f (
ν
−
ν i ) Si
0
-1
Ii =
0 i
,where ν is the excitation wavenumber in cm , ν the wavenumber of the i-th
ν i
[
1− exp
(
− hcν i kT
)]
normal mode, h, c, and k the universal constants, and f the normalization factor.
The theoretical IR and Raman spectra were simulated using calculated frequencies and intensities
-1
with bands having a Lorentz shape and half-width of 10 cm using Swizard software [33]. The normal
vibration assignment was performed by calculating the potential energy distribution [34]. To evaluate
the chemical properties of calixarenes, natural bonding orbitals, chemical potential, and electrophilicity
index were calculated [35, 36].
4
. Results and discussion
The calculation has shown that the isolated TB4 and SC4 molecules take a cone conformation
according to experimental X-ray data [27,38]. The calculated bond lengths of SC4 are in agreement with

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4
the experimental data on X-ray diffraction (Supplementary information S1) [27]. Despite the fact that
the distances between the neighboring oxygen atoms differ slightly from one another in calculation and
experiment, the four pairs of hydrogen bonds forming a cyclic system in TB4 and SC4 may be
considered equivalent (Supplementary information S1). The average values of the distances calculated
between the neighboring oxygen atoms in TB4 and SC4 are 2.65 and 2.64 Å, respectively, and
...
correspond to the experiment [27,37]. The average values of the theoretical angles O−H O in TB4 and
SC4 are equal to 164.6 and 162.5°. The size of the calixarene cavity determines their ability to extract
metals. The distance between the opposite oxygen atoms in the macrocycle in TB4 and SC4 is 3.7 Å. As
a result, these molecules have a cavity large enough to accommodate the guest molecules.
Table 1 shows the relative free energies and dipole moments of the cone, pcone, 1,2-alt and 1,3-
alt conformers of SC4 and TB4 molecules. The most stable and polar is the conformation of the cone
with four intramolecular cooperative hydrogen bonds. As the number of hydrogen bonds decreases, the
free energy of conformers decreases (Table 1, Fig. 2). There is a sharp increase in the polarity of the SC4
molecule in comparison with the tert-butyl analogue.
To estimate the electrical properties of the molecules, we calculated the charge distribution on
the SC4 atoms and compared them to the corresponding amounts in TB4 (Table 2). As a result, the
calixarene molecules TB4 and SC4 contain polar OH bonds with natural atomic charges [34] (in e) on
the O atoms (-0.761 and -0.751) and H (0.528 and 0.531), respectively. The sulfonyl group has charges
on the O atoms (-0.934, -0.914 and -0.923) and S (2.403) respectively.
For SC4 molecules, torsion angles φ(C7−C6−C40−C37) and χ(C6−C40−C37−C36) are used as
conformation parameters [39]. The mean values of the calculated torsion angles φ and χ are -92.3º and
9
2.0º and are in agreement with the experimental values 91.7 and 85.3º (Table 1) [27]. In the TB4
molecules, the mean values of the calculated parameters φ and χ are equal to -91.0º and 91.5º and do not
differ much from the corresponding values for SC4. Thus, the orientation of the aromatic moieties of the
calixarenes does not change when the tert-butyl group is replaced by the sulfonate group.
Figs. 3-6 and Supplementary information S2, S3 show the experimental and calculated
vibrational spectra of TB4 and SC4. To interpret the vibrational spectra of TB4 and SC4, we calculated
the potential energy distribution (PED). The assignment of the bands in the spectra was carried out by
considering the displacements of the atoms under oscillations. A comparison of the vibrational spectra
of TB4 and SC4 makes it possible to distinguish the bands associated with the vibrations of the sulfonyl
groups (Fig. 3).

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5
The calculation of the molecules in the conformation of the cone makes it possible to understand
the main characteristics of the experimental IR and Raman spectra of TB4 and SC4. The theoretical
absorption and scattering curves of isolated molecules, TB4 and SC4, are simpler than the experimental
IR and Raman spectra of crystalline samples in which band shifts and splits occur. Each vibration of the
phenolic fragment causes four vibrations of the TB4 and SC4 molecules. The theoretical curves for cone
conformation best fit the IR and Raman SC4 experimental spectra. The intensities of certain bands in the
experimental and calculated IR and Raman spectra are substantially different. These differences may be
due to the imperfection of the model and to the approximation chosen for the calculation.
IR spectroscopy is a practical method for studying hydrogen bonds (Fig. 3). There is no band of
free OH groups in the IR spectrum, which means that all the hydroxyl groups participate in the
formation of hydrogen bonds and that the TB4 and SC4 molecules occupy a conformation of the cone.
-1
Band 3159 cm in the IR spectrum of TB4 refers to stretching vibrations of the hydroxyl groups. The
-1
3
371 cm band of the SC4 IR spectrum refers to the OH stretching vibrations of the polar SO H groups
3
-1
participating in the H-bond with the water molecules in the calixarene cavity. The 3188 cm band is due
to oscillations of the OH groups along the lower rim of the molecule. The magnitude of the νOH
frequency indicates that in the presence of polar sulfonate groups in SC4, the hydrogen bond weakened
relative to TB4.
-1
In the region 3200-2800 cm of the IR and Raman experimental spectra of SC4, there are bands
of CH stretching vibrations (Fig. 3,4). Stretching the CH bond vibrations of aromatic moieties causes
-1
weak bands at 3053, 3033 cm in the Raman spectrum of SC4. The asymmetric and symmetrical
-1
stretching vibrations of the methylene groups appear as lines 2981, 2957 and 2883 cm of the SC4
-1
Raman spectrum. The 2959 and 2870 cm bands are observed in the IR spectrum of TB4 and are related
to CH stretching vibrations of the tert-butyl groups.
-1
The bands 1613, 1594 cm of the stretching vibrations of the CC bonds and the bending
vibrations of CCH of aromatic fractions appear in the Raman spectrum of SC4. These vibrations show
-1
the band at 1599 cm in the IR spectrum of SC4. The asymmetric deformation vibrations of the
-1
-
methylene groups result in bands at 1472, 1460, 1429 cm in the IR spectrum and 1488, 1480, 1460 cm
1
-1
bands in the SC4 Raman spectra. These oscillations give rise to the band at 1470 cm in the IR
spectrum of TB4.
-1
The band at 1397 cm in the IR spectrum of SC4 refers to the stretching vibrations of the CC
bonds of the aromatic fragments and the HCH and COH bending vibrations. The stretching vibrations of

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6
-1
the SO bonds cause a band at 1375 cm in the SC4 IR spectrum. The stretching of the CC bond
-1
vibrations of the aromatic moieties causes the appearance of bands at 1305 cm in the IR spectrum and
-1
at 1312 cm in the Raman spectrum of SC4. The stretching vibrations of CO bonds induce bands at
-1
-1
1
285 cm in the IR spectrum and at 1287 cm in the Raman spectrum of SC4. The medium intensity
-1
band in the SC4 IR spectrum at 1270 cm is due to stretching vibrations of CC and CO bonds. The
-1
stretching vibrations of CC bonds show bands at 1248, 1202 cm in the IR spectrum of TB4 and at
-1
1
246, 1216 cm bands in the IR spectrum of SC4.
-1
The intense bands at 1156, 1123, 1105, 1040 cm in the SC4 IR spectrum belong to the
-1
stretching vibrations of the sulfonyl groups. The band at 1119 cm in the IR spectrum of TB4 is due to
the CH in-plane deformation vibrations of the aromatic moieties. Stretching vibrations of CC bonds and
-1
CCH bending vibrations appear as bands at 870 and 972 cm in the IR spectra of TB4 and SC4. The
-1
-1
8
18, 783 cm bands in the infrared spectrum of TB4 and the 935, 903 cm bands in the SC4 IR spectrum
relate to non-planar vibrations of aromatic groups. The rocking vibrations of the methylene groups show
-1
the band at 897 cm of the SC4 IR spectrum. The twisting vibrations of the CH
2
groups cause bands at
-
1
8
7
15, 833 cm in the SC4 IR spectrum. The stretching vibrations of SO bonds give bands at 765, 774,
-1
88 cm in the IR spectrum of the SC4.
The torsional oscillations around the CC links cause the bands at 742, 672, 660, 628 cm in the
SC4 IR spectrum. The deformation vibrations of the sulfonate groups appear as bands at 599, 472,
-1
-1
4
49 cm in the IR spectrum of SC4. The torsional vibrations of the benzene rings and the deformation
-1
vibrations of the macrocycle causes bands at 517, 442, 416, 395 cm in the IR spectrum of SC4. The
-1
bands at 415, 356, 320, 290, 269, 203, 133 cm in the SC4 Raman spectra are associated with
deformations of the skeletal angles and torsion vibrations of the sulfonate groups.
Comparing the IR spectra of TB4 and SC4 allows you to select bands of sulfonate groups. The
-1
strong band at 1479 cm in the IR spectrum of TB4 corresponds to the medium intensity band at
-1
-1
1
472 cm in the SC4 IR spectrum. The bands at 1391 and 1368 cm of the IR spectrum of TB4
-1
correspond to the band at 1375 cm of the IR spectrum of SC4. It is interesting to note that the relative
intensities of a whole series of bands in the IR spectra of TB4 and SC4 differ significantly.
For analytical purposes, it is important to determine how the replacement of tert-butyl groups by
sulfonate groups is reflected in the IR spectra (Fig. 3). In the region of CH stretching vibrations in the
-1
TB4 IR spectrum, bands of tert-butyl groups at 2959, 2909 and 2870 cm are observed. They

ACCEPTED MANUSCRIPT
7
-1
correspond to the bands at 2955 and 2874 cm bands in the SC4 IR spectrum. The relative intensities of
these bands in the IR spectra of TB4 and SC4 differ considerably.
-1
In the middle region of the IR spectrum of the TB4 bands, 1391, 1368, 1296, 1202, 818 cm
characteristic of the tert-butyl substituent are observed. These bands are absent in the SC4 IR spectrum.
-1
Conversely, the bands at 1375, 1270, 1216, 1156, 1123, 1105, 1040 cm observed in the IR spectrum of
SC4 are absent in the IR spectrum of TB4.
Thus, the aromatic fragments show the lines of stretching vibrations of CC bonds at 1613,
-1
-1
1
594 cm bands in the SC4 Raman spectrum. The methylene groups have 2957, 2883 cm bands in the
-1
Raman spectrum. The sulfonate groups have bands at 1156, 1123, 1105, 1040 cm in the SC4 IR spectra
associated with S−O stretching vibrations.
According to the results of the calculations, it is possible to follow the modifications of the IR
and Raman spectra for four possible conformations of the SC4 molecule. The analysis of the theoretical
vibrational spectra shows that with the reorientation of the aromatic fragments, a change in the intensity
of a certain number of bands occurs (Figs. 4,5, Supplementary information S3). Bands at 1342, 1116,
-
1
-1
-1
7
7
64 cm (cone), 1305, 1202, 792 cm (pcone), 1339, 1163, 782 cm (1,2-alternate), 1333, 1124,
-1
86 cm (1,3-alternate) were selected for the analytical purposes.
The calixarenes molecules are in the conformation of the cone. In general, the crystallization of
such samples from their solutions results in the capture of a portion of the solvent molecules. These
guest molecules are in sorbate, solvate or clathrate forms and differentiated by their intermolecular
interactions. Using thermal analysis methods, we tried to analyze the processes occurring in the
calixarenes during heating. To our knowledge, no work simultaneously using the FTIR spectroscopy and
thermal analysis methods to study the processes involved in heating calixarenes had been conducted.
In fact, by analyzing the TGA curve of TB4 (Fig. 7), it can be seen that a significant change in
sample mass occurs at temperatures above 356° C. According to the TGA data in the temperature range
of 100 to 336° C, there is a slight decrease in the mass of the sample (Fig. 7). A minor loss of mass (up
to 3 to 4% of the sample mass) is probably due to the elimination of small molecules. Such an
insignificant number of these small molecules in the crystals is explained by the fact that the tert-butyl
groups of the TB4 molecule can partially penetrate the cavity of another calixarene molecule preventing
the entry of small molecules.
In the case of SC4 calixarene, unlike non-polar t-Bu groups, polar sulfonate groups attract much
more water molecules of all three types. A loss of mass close to 20% occurs up to 200° C in two stages,

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8
it is likely that it is adsorbed water, and more firm retained molecules of different types (Supplementary
o
o
information 4: DTG peaks at 81 and 141 C, respectively). The third step of about 300° C is associated
with the separation of the sulfonate groups and the destruction of the calixarene structure. The Fig. 7
shows the IR spectra of the gas phase released at different temperatures. All bands perfectly match the
IR spectrum of the sulfur dioxide. The color of the calixarene sample ranges from white at room
temperature to slightly yellow at 220° C and black at 290° C. As the temperature increases, the intensity
of the bands of the sulfonate groups in the SC4 IR spectra decreases (Fig. 8). Therefore, the destruction
of the p-sulfonatocalix[4]arene begins with the sulfonate groups.
During heating, the reorganization of hydrogen bonds occurs in the supramolecular system of p-
sulfonatocalix[4]arene-water. There is a change in the contour of the OH stretching vibrations band in
-1
-1
the SC4 IR spectra. The band at 3188 cm in the SC4 IR starting spectrum, increases to 3235 cm after
-1
heating to 200° C, and becomes a shoulder at 3250 cm , at a temperature of 300° C, its intensity
-1
substantially reduces. Adsorbed water gives bands at 3370-3400 cm in the three IR spectra.
In this article, we have also tried to characterize the reactivity of calixarenes using global
descriptors. The introduction of sulfonyl groups into calixarene increases the ionization energy, electron
affinity, chemical potential, dipole moment, and electrophilic index relative to TB4 (Table 3). Analysis
of the molecular orbitals in the SC4 molecule showed that HOMO and LUMO consist of π orbitals (Fig.
9
). HOMO and LUMO cover aromatic units with notable conjugation and sulfonate groups.
When forming hydrogen bonds, there is a change in the electron density in the molecules. The
NBO approximation takes into account the transfer of the electron density from the donor to the
acceptor. During the formation of the hydrogen bond, electron density transfer from a lone electron pair
of oxygen to the antibonding orbital of the OH bond takes place. The hyper-conjugated interaction
between the lone electron pair of oxygen as a donor and the antibonding orbital of the OH bond as an
acceptor was detected, thus ensuring charge transfer from the first to the second. As can be seen from
our data, the SC4 molecule has a complex pattern of hydrogen bonding interactions:
1 1 2 2 2 2
n(LP O1)→σ* (O4–H44), n(LP O1)→σ* (O4–H44), n(LP O1)→σ* (C5–C10) with stabilization
energies equal to 15.63, 13.56 and 19.61 kcal/mol (Supplementary information S5). In aromatic
moieties, conjugation bonds participate in interactions σ (C5–C10) → σ* (C6–С7), σ (C5–C10) →
2
2
2
2 2 2
σ* (C8–С9), σ (C5–C10) with energies equal to 17.38, 24.82 and 22.98 kcal/mol. The
(C6–C7) → σ*
sulfonate groups interact with aromatic moieties σ (C8–C9) → σ* (S54–O56) with an energy
2
1
6
.56 kcal/mol.

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9
5
. Summary
The calculation of the potential energy distribution enabled us to perform a band classification in
the IR and Raman experimental spectra. A complete interpretation of the calixarene spectra has been
proposed based on experimental data and quantum calculations. The study of tert-butyl and sulfonato
derivatives of calix[4]arenes by FTIR spectroscopy showed that there was no absorption band for the
free hydroxyl groups and that an intramolecular hydrogen bond was produced. The hydrogen bond in
SC4 is weaker than in TB4.
The destruction process of the studied calixarene TB4 and SC4 samples are very different. TB4
barely loses mass up to a temperature of 400° C. In SC4, the loss of mass occurs in two stages: up to
2
00° C, it is most likely water from the cavity of a molecule. The second step of about 300° C is
associated with the separation of the sulfonate groups and the destruction of the calixarene structure.
Acknowledgement
We thank the Russian Science Foundation for the financial support of this work (project № 19-
7
3-20035). The authors are grateful to the Assigned Spectral-Analytical Center of FRC Kazan Scientific
Center of RAS CSF-SAC FRC KSC RAS for technical assistance in research.

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2
Figure captions
Fig. 1. Structure of p-tert-butylcalix[4]arene (a) and p-calix[4]arene sulfonic acid (b).
Fig. 2. Optimized geometry and atom numbering for p-calix[4]arene sulfonic acid in the conformation
cone (1), partial cone (2), 1,2-alternate (3) and 1,3-alternate (3).
Fig. 3. Experimental IR spectra of p-calix[4]arene sulfonic acid (1) and p-tertbutylcalix[4]arene (2).
Fig. 4. Experimental Raman spectra of p-calix[4]arene sulfonic acid.
Fig. 5. Experimental (1) and theoretical IR spectra of p-calix[4]arene sulfonic acid in the conformation
-1
cone (2), partial cone (3), 1,2-alternate (4) and 1,3-alternate (5) in the region 1800-400 cm .
Fig. 6. Experimental (1) and theoretical Raman spectra of p-calix[4]arene sulfonic acid in the
-
conformation cone (2), partial cone (3), 1,2-alternate (4) and 1,3-alternate (5) in the region 1800-400 cm
1
.
Fig. 7. TGA heating curves of samples of p-calix[4]arene sulfonic acid (SC4) and p-
tertbutylcalix[4]arene (TB4) molecules from room temperature to 600° C. The inset images show the
three IR spectra of the gas phase released during a) 220 ° C, (b) 290 ° C, (c) 400 ° C.
Fig. 8. IR spectra of p-calix[4]arene sulfonic acid heated at 300° C (1), 200° C (2) and at room
temperature (3).
Fig. 9. Molecular orbital surfaces of p-calix[4]arene sulfonic acid.

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Table 1
Relative Gibbs free energy ꢀG (kcal/mol), dipole moments ꢁ (D), and dihedral angles
a
φ, χ (in degrees) of conformers of p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene
calculated in the DFT/B3LYP 6-31G(d,p) level
Conformation ꢀG
ꢁ
φ1
χ1
φ2
χ2
φ3
χ3
φ4
χ4
SC4
Cone
Partial cone
0.0
5.60
9.40
12.4 -92.3
92.0
85.6
-92.3 92.0
-116.6 -145.6 82.1
-92.3 92.0
-92.3 92.0
5.8
6.6
-96.7
-110.4
120.3
-132.7 -137.6 87.7
1
1
,3-Alternate
,2-Alternate
-113.4 111.1 114.7 -111.4 -113.9 111.7 114.8
142.6 -80.3 97.8
10.08 5.4
-103.6 80.5
-91.0 91.5
-126.8 -132.1
-91.0 91.5
TB4
Cone
Partial cone
0.0
8.41
14.11 0.0
15.13 1.7
2.6
1.8
-91.0
91.5
106.5 41.6
-91.0 91.5
-168.1
-118.1
-98.4
-150.0 -170.5 -161.7 -60.5 -118.5
1,3-Alternate
-129.5 118.1 129.5 -118.1 -129.5 118.1 129.5
84.4 -113.1 -146.6 82.3 -133.4 -138.0 88.8
1,2-Alternate
a
Dihedral angles φ - С(7)–C(6)–C(40)–C(37), χ - C(6)–C(40)–C(37)–C(36), φ -
1
1
2
C(34)–C(33)–C(31)–C(28), χ - C(33)–C(31)–C(28)–C(27), φ - C(25)–C(24)–C(22)–
2
3
C(19), χ - C(24)–C(22)–C(19)–C(18), φ - C(16)–C(15)–C(13)–C(10), χ - C(15)–C(13)–
3
4
4
C(10)–C(9)

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Table 2
The partial charges of the atoms determined by natural population analysis of p-tert-
butylcalix[4]arene and p-sulfonatocalix[4]arene
TB4
SC4
Atom qn
Atom qn
O1
-0.761 O1
-0.751
C5
0.323 C5
-0.067 C6
-0.219 C7
-0.036 C8
-0.215 C9
-0.058 C10
0.528 H41
-0.674 O53
-0.061 S54
-0.689 O55
-0.675 O56
H69
0.350
-0.063
-0.192
-0.343
-0.191
-0.072
0.531
-0.934
2.403
-0.914
-0.923
0.522
C25
C21
C17
C13
C9
H46
С49
С33
C53
C57

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Table 3
Global reactivity descriptors of p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene
System
Ionization Electron
energy, eV affinity,
eV
Chemical
potential,
eV
Softness,
eV
Electrophilicity Dipole
index, eV
moment,
D
TB4
SC4
6.75
8.16
-0.71
1.21
-3.02
-4.69
0.13
0.14
1.22
3.16
1.00
4.89

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(1)
(2)

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(3)
(4)

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2
1
0
1
2
3
200
1600
1200
800
400
-
1
Wavenumber/cm

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1
00
50
0
3
200 3000 280018001600140012001000 800 600 400 200
-1
Wavenumber/cm

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5
4
4
3
3
2
2
1
1
0
0
.0
.5
.0
.5
.0
.5
.0
.5
.0
.5
1
2
3
4
5
.0
1
800
1600
1400
1200
1000
800
600
400
-1
Wavenumber/cm

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5
4
4
3
3
2
2
1
1
00
50
00
50
00
50
00
50
00
1
2
3
4
5
50
0
1
800 1600 1400 1200 1000 800
600
400
200
-1
Wavenumber/cm

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3.0
2.5
2.0
1.5
1.0
0.5
0.0
1
2
3
3600
3200
2800
1500
1000
500
-1
Wavenumber/cm

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HOMO
LUMO

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>
>
The FTIR and FT-Raman spectra of p-sulfonatocalix[4]arene were studied.
>
Normal mode analysis were performed for p-sulfonatocalix[4]arene.
The IR and Raman spectra of p-sulfonatocalix[4]arene were calculated and interpreted.