Experimental comparative study of dynamic behavior in solution phase of C-Tetra(phenyl)resorcin[4]arene and C-Tetra(phenyl)pyrogallol[4]arene

Article abstract of DOI:10.3390/molecules25102275

The synthesis of phenyl-resorcinarenes and pyrogallolarenes is known to produce a conformational mixture of cone and chair isomers. Depending on the synthesis conditions the composition of the conformational mixture is variable; however, the cone conformer is the greatest proportion of phenyl-resorcin[4]arenes and chair conformer of pyrogallol[4]arenes. The experimental evidence suggests that phenyl-substituted resorcinarene and pyrogallolarene exist as a dynamic boat in solution.

Full text of DOI:10.3390/molecules25102275

Article
Experimental Comparative Study of Dynamic Behavior
in Solution Phase of C-Tetra(phenyl)resorcin[4]arene
and C-Tetra(phenyl)pyrogallol[4]arene
José Luis Casas-Hinestroza, Miguel Ángel Vela Suazo and Mauricio Maldonado Villamil *
Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia-sede Bogotá,
Carrera 30 # 45-03, Bogotá 111321, Colombia; jlcasash@unal.edu.co (J.L.C.-H.);
mvela@unal.edu.co (M.Á.V.S.)
*
Correspondence: mmaldonadov@unal.edu.co; Tel./Fax: +57-1-316-5000
Received: 11 March 2020; Accepted: 8 May 2020; Published: 12 May 2020
Abstract: The synthesis of phenyl-resorcinarenes and pyrogallolarenes is known to produce a
conformational mixture of cone and chair isomers. Depending on the synthesis conditions the
composition of the conformational mixture is variable; however, the cone conformer is the greatest
proportion of phenyl-resorcin[4]arenes and chair conformer of pyrogallol[4]arenes. The
experimental evidence suggests that phenyl-substituted resorcinarene and pyrogallolarene exist as
a dynamic boat in solution.
Keywords: polyhydroxylated platform; conformational behavior; conformers; dynamic studies;
dynamic boat
1
. Introduction
Among the macromolecules there are specific groups with chemical and structural
characteristics that have attracted attention in recent years in different fields of research. An
interesting example is the Calixarenes family—in particular resorcinarenes and pyrogallolarenes
[1]—which can be obtained by reactions between aldehydes and resorcinol or pyrogallol,
respectively, the latter being the main difference between the two types of macrocycles (Scheme 1).
Using different phenols for the synthesis leads to different properties; for example, resorcinarenes
have two active sites on the upper rim (position 2 and hydroxyl groups), where the macromolecule
can be functionalized or derivatized. A different case occurs with pyrogallolarenes, which only have
hydroxyl groups on the upper rim, which restricts their derivation possibilities somewhat as
compared with resorcinarenes. In both cases, the cyclocondensation reaction is performed under acid
catalysis conditions [2–4], which has the advantage of a low cost together with a minimum of
synthetic steps, in addition to a minimum variation in the synthetic design of the macrocyclic
molecules with different chemical functions [5].
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Scheme 1. Synthesis of resorcinarenes and pyrogallolarenes.
An interesting aspect of this type of compound is that it can adopt different structural isomers.
This often depends on the reaction conditions or the type of aldehyde used and the reaction time [6].
Among the most prominent isomers are those of the cone and boat type, thanks to the fact that they
are more stable and are usually obtained in greater proportion when the synthesis is carried out [7,8].
The influence of the substituent on the lower rim can influence the type of conformation that can be
obtained. In this way, resorcinarenes with aliphatic substitutions on the lower rim exhibit the same
cone-type isomers as the majority, while the resorcinarenes that have aromatic substitutions show
cone-chair-type isomeric mixtures, in which their relationship varies depending on the synthesis
conditions [9]. With respect to pyrogallolarenes, the products obtained in the synthesis with aliphatic
aldehydes show a tendency for the formation of cone isomers in greater proportion. On the other
hand, those synthesized from aromatic aldehydes show a preference for producing chair-type
isomers [10,11]. Even so, as with resorcinarenes, there are some cases where the tendency changes or
an isomeric mixture is produced, depending on the synthesis conditions [12].
The cone and boat isomers have structural properties that have been beneficial in the vast majority
of applications, due to the fact that these forms have an electron-rich cavity [13], which can interact
with other molecules or analytes in such a way that they can stay within these macrocycles. Another
important feature is that their hydroxyl groups, both in resorcinarenes and pyrogallolarenes, have an
upward orientation, which sometimes can form supramolecular assemblies through hydrogen
bonds, such as capsules or aggregates. These bonds commonly established between the upper edges
of resorcinarenes or pyrogallolarenes are not unique forms such as supramolecular structures—there
are also assemblies where agents such as solvents [14], coordinating metals [15,16] and covalent
bonds [17,18] exist. There are several applications where resorcinarenes and pyrogallolarenes have
contributed to significant advances, basically due to their versatility, both in synthesis and derivatives
and in their molecular structure itself. A field where they have been widely used is host-guest systems
[
19–21], since the electron-rich cavity of cone-type isomers allows different types of interactions with
molecules [22] to be established, especially with tetraalkylammonium-type salts or metal cations
23,24]. This has led to different areas of applications, such as sensors [25], catalysis [26,27], heavy
[
metal complexes for purification of water tributaries [28–30] and chemical separations by
modification of Hight Performance Liquid Chromatography (HPLC) columns [31–34], among
others.
The aforementioned applications are possible because the polyhydroxylated platforms undergo
conformations and conformational interconversions in solution [35], which allows host-guest
interactions. For example, the conformation of resorcinarenes can be rigidified into a cone by linking
the hydroxyl groups of the upper rim, which provides a higher degree of preorganization.
Nevertheless, in solution the rccc isomer may adopt cone and boat conformations [36–38], which

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interconvert rapidly at room temperature. Studies of the conformational properties of resorcinarenes
modified on the lower rim show that the most stable conformer in solution is cone and this trend is
favored by bulky substituents in the macrocyclic ring [39].
Continuing with our studies of the structure of polyhydroxylated platforms [12,33,40,41], we
found that the bulky aromatic substituents on the lower rim of polyhydroxylated platforms in cone
conformation exhibited a dynamic behavior, which stimulated interest in examining the
conformational preferences. For this purpose, in this article, the comparative behavior of C-
tetra(phenyl)-resorcin[4]arene (1) and C-tetra(phenyl)pyrogallol[4]arene (2) compounds is studied
1
13
1
using H-NMR and C-NMR data and dynamic H-NMR spectra.
2
. Results and Discussion
2
.1. Synthesis and Separation of Conformers
As mentioned in the introduction, we chose C-tetra(phenyl)-resorcin[4]arene (1) and C-
tetra(phenyl)pyrogallol[4]arene (2) in order to explore the dynamic behavior of cone conformers in
dimethyl sulfoxide and acetonitrile. In this way, the obtaining of 1 and 2 was done according to the
procedure described in the literature, through the acid-catalized cyclocondensation of benzaldehyde
with resorcinol or pyrogallol, respectively [8,9]. The synthesis was carried out through the acid-
catalyzed cyclocondensation of phenol with benzaldehyde in ethyl alcohol at reflux condition. In the
reaction (Scheme 2), two products were obtained (Supplementary Material, Figures S1 and S10, which
were used for dynamic nuclear magnetic resonance (NMR) studies after separation.
Scheme 2. Synthesis of tetra(phenyl) pyrogallol[4]arene and resocin[4]arene.
1
In the H-NMR spectrum of 1a (Figure S3), individual assignments of the protons were made
based on their positions, multiplicities, integral values and comparison of spectral data with reported
1
values of similar compounds [12,40]. In this way, the H-NMR spectrum of 1a displayed the
characteristic signal of a methine bridge at 5.63 ppm. In the aromatic region, normally the ortho- and
meta-protons of resorcinarene moiety attached to a hydroxyl group produce separate signals and the
ortho-protons are shielded by hydroxyl groups, while the meta-protons are unshielded and resonate
in the upfield region. Given this, the hydrogen of the tetrasubstituted resorcinol units appears at 6.32
and 6.15 ppm, respectively. The signals at 6.97 and 6.75 were attributed to the hydrogen in the
aromatic ring of the phenyl substituent on the lower rim. Finally, the signal at 8.53 ppm was assigned
to hydroxyl groups in the molecule. As mentioned above, resorcinarenes can exist in conformations
1
of various symmetries; in this way, in the first product formed the H-NMR showed the characteristic
signals for the cone conformation (diastereomer rccc). Initially in our case, the signals indicate the
1
existence of highly symmetric cone conformation in solution if the H-NMR spectrum of 1a is
1
recorded at 333 K but if the H-NMR spectrum of 1a is recorded at room temperature, the signals
allowed inferring the presence of other conformations, as will be analyzed later. The 13C-NMR
spectrum in DMSO-d
6
(figure S4) exhibited nine signals, which agree with the structure of compound
1
a, that is, it displayed eight signals for the aromatic systems and the signal at 41.6 ppm confirmed
the presence of a methyne-bridge fragment between the aromatic rings, signal assignment was
confirmed using the 2D-NMR-HSQC spectrum (Figure S5).
The second product 1b, obtained in the synthesis, exhibited absorptions for C-O stretching (1159
−
1
−1
−1
cm ), an aromatic ring (1614 cm ) and the hydroxyl groups (3318 cm ) in the FT-IR spectrum (Figure
1
S7). The H-NMR spectrum (Figure S8) displayed the characteristic signal of a methine-bridge

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fragment between the aromatic rings (5.56 ppm) and the aromatic hydrogen of the tetrasubstituted
resorcinol unit at 6.12 and 6.22 ppm for the protons in the ortho position and the signal at 6.61 ppm
for meta-protons, the signals at 6.84 were attributed to the hydrogen in the aromatic ring of the phenyl
substituent on the lower rim. Finally, the signals at 8.57 and 8.46 ppm were assigned to two types of
1
3
hydroxyl groups in the molecule. The signals observed in C-NMR spectrum are consistent with the
structure (Figure S9).
The reaction of pyrogallol with benzaldehyde was carried out under the same conditions. After
1
2 h in reflux, Thin Layer Chromatography (TLC) analysis of the reaction mixture showed two
products corresponding to the conformational mixture—cone (2a) and chair (2b) (Figure S11). Then
the separation of cone and chair conformers was carried out by using the solvent-extraction technique.
1
The H-NMR spectrum of product 2a (Figure S13) exhibited two single peaks, at 7.77 and 7.65
ppm, corresponding to two classes of hydroxyl groups, signals corresponding to the pyrogallol
residues—the first signal corresponds to a hydroxyl group in position 2 and the second signal for the
hydroxyl group in positions 1 and 3. Additionally, all the patterns were consistent with the structure
of the expected cone conformer 2a. On the other hand, the spectrum of product 2b (Figure S17)
exhibited four different hydroxyl moieties, at 7.86, 7.67, 7.56 and 7.45 ppm, corresponding to two
classes of hydroxyl groups attached to pyrogallol residues in the macrocyclic system. Careful analysis
of all the patterns confirmed the structure of chair conformer 2b. The increase of signals in the 13C-
NMR spectrum also confirmed the chair conformation (Figure S18). A comparison of the NMR
spectra for the two isomer types is shown in Figure 1.
1
Figure 1. Comparative H-NMR spectra of de products 2a and 2b in DMSO-d
6
at room temperature.
1
2
.2. Dynamic H-NMR Studies
1
As mentioned above, if the H-NMR spectrum in DMSO-d
6
of 1a was recorded at room
temperature, the signal in the aromatic region at 6.32 ppm was observed as a broad signal. This fact
was interesting, because this behavior is characteristic of a dynamic system in solution. In order to
1
establish this behavior in DMSO-d
6
initially, the H-NMR spectrum was recorded at a temperature of
3
33 K (Figure 1), observing that this signal was better defined, so it was decided to perform a dynamic
study at variable temperature. As shown in Figure 2, at the lowest temperature, the spectrum of
Compound 1a in the aromatic region (resorcinol residue) exhibited four signals—two for aromatic

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protons on the upper rim at 6.55 and 6.20 ppm and two signals for the protons on the lower rim at
.00 and 6.15 ppm.
6
Figure 2. Dynamic study of tetra(phenyl)-resorcin[4]arene (1a) in MeCN-DMSO-d
6
mixture.
1
The H-NMR spectra of conformer 1a at 253.15 K was consistent with the presence of two
conformers that exhibited two resonances for a flattened ring and two resonances for an opposite
ring. This observation prompted a detailed study of the NMR spectra. It has been well established
that the conformation of the resorcinarene skeleton can be assigned in solution by a comparison of
the chemical shift for the arene resonance in other analogues macrocycles, because the protons in the
flattened ring are more shielded. In this way, flattened cone A and flattened cone B (Figure 3) are
possible conformations in DMSO-d for this macrocyclic system, which is confirmed by other areas
6
of the spectrum, which are consistent with this conformational assignment. In the same way, in
DMSO, the spectrum obtained at 268.15 K shows coalescence of the peaks in the aromatic zone,
particularly for resorcinol ring signals, confirming a very dynamic interconversion system between
the conformers flattened cone A and flattened cone B.
At other temperatures (283.15, 298.15 and 333.15 K), aromatic protons in ortho- and meta-
positions of the resorcinol unit are sensitive to the chemical environment of the different
conformations, as has been observed in other similar systems and is favored by the interaction with
1
the solvent. In this way, the H-NMR spectrum of 1a in DMSO showed mixed conformations,
according to the following signals—two protons in the aromatic region (6.32 and 6.15 ppm) indicate
a high degree of conformational equilibrium between cone and flattened cone (A and B) conformers
for diastereomer rccc (Figure 3).

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Figure 3. Dynamic behavior of 1a and 2a.
1H-NMR spectrum of 2a in DMSO-d
at 293.15 K is characteristic of the cone conformation and
6
this change when the temperature decreases (Figure 4). At 248.15 K, the spectrum showed two
resonances consistent with the presence of two conformers—flattened cone A and flattened cone B
(Figure 3), which showed one resonance at 6.00 ppm for a flattened pentasubstituted pyrogallol unit
and one resonance at 6.60 ppm for an opposite pentasubstituted pyrogallol unit and the spectrum
obtained at 273.15 K shows coalescence of these peaks in the aromatic zone. Similarly, and as seen
with compound 1a, these observations suggest that the compound exists in two forms in solution,
cone and flattened cone conformers. In DMSO-d , 1b showed a similar pattern of signals and this
6
confirms the presence of the two conformers with very small differences with respect to their
coalescence temperatures.
Figure 4. Dynamic study of tetra(phenyl)-pyrogallol[4]arene (2a) in MeCN-DMSO-d mixture.
6
According to the known experimental evidence for aliphatic resorcinarenes and
pyrogallolarenes, those exhibit a rigid cone(rccc) structure at room temperature in solution and solid
state [42,43] which is established due to the intramolecular hydrogen bonds in the upper rim. In
contrast with the behavior of platforms with aliphatic substituent, the experimental evidence for
platforms 1a and 1b showed that they have a dynamic behavior in solution, this behavior can be due

Molecules 2020, 25, 2275
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to loss of intramolecular hydrogen bonds on the upper rim, the existence of π-π interactions of the
aromatic system in the lower rim and polar··· π, C-H···π [44,45] between solvent molecules and
aromatic system permitting a temporal rearrangement of the macrocycle.
3
. Materials and Methods
Infrared (IR) spectra were recorded on a ThermoFisher Scientific Nicolet iS10 Fourier transform
infrared (FTIR) spectrometer with a monolithic Diamond, Attenuated Total Reflection (ATR)
accessory and absorption in cm−1 (Thermo Scientific, Waltham, MA, USA). H and C-NMR spectra
were recorded at 400 MHz on a Bruker Advance 400 instrument. Molar mass was determined with
Agilent 6470 triple quadrupole mass spectrometer. RP–HPLC analyses were performed on a
Chomolith® C18 column (Merck, Kenilworth, NJ, USA, 50 mm), using an Agilent 1200 Liquid
Chromatograph (Agilent, Omaha, NE, USA). Chemical shifts are reported in ppm, using the solvent
residual signal. Melting points were measured on a Stuart apparatus (Cole-Parmer, Stafford, UK) and
are not corrected. The elemental analysis for carbon and hydrogen was carried out using a Thermo
Flash 2000 elemental analyzer (Thermo Scientific, Waltham, MA, USA).
1
13
3
.1. Synthesis of Tetra(phenyl)-pyrogallol[4]arene and Resorcin[4]arene
Synthesis of C-tetra(phenyl)-pyrogallol[4]arene. A Pyrogallol solution (5 mmol) in 10 mL of
ethanol was added dropwise to 0.4 mL of concentrated chlorine acid (37%), the mixture was stirred
º
at 0 C for 5 min and then 0.5 mL of benzaldehyde (5 mmol) was added dropwise. After 10 min, the
mixture was heated to 70–80 °C and refluxed for 12 h and the solid precipitate was filtered and
washed with a mixture of water and ethanol (1:1), producing a pink solid (569 mg) at 56% yield,
1
13
which was characterized by means IR, H-NMR and C-NMR and used for separation experiments.
Conformation separation. The separation of boat and chair conformers was carried out by using
the solvent-extraction technique with mixtures of solvents such as ethyl acetate, water and ethanol.
The crude mixture (200 mg) was stirred in 10 mL of a mixture of solvents (ethyl acetate, ethanol and
water, at a ratio of 2:1:1, respectively) for 10 min and the suspended solid was separated by filtration,
dried and used for conformational studies, whereupon it was determined to be in the chair conformer
configuration. The mixture of solvents was removed by evaporation, resulting in a second red solid
that exhibited the boat conformation.
−1
C-tetra(phenyl)pyrogallol[4]arene (boat) m.p. > 350˚C IR (ATR/cm ): 3300–3600 (broad), 1630, 1500,
−1 1
1
464, 1368, 1282, 1247, 1209, 1064, 1015, 163, 699, 566, 416 cm ; H-NMR (400 MHz, DMSO-d
s, 4H, OH); 7.65 (s, 8H, OH); 6.95–6.96 (m, 12H, Ar); 6.76–6.77 (m, 8H, Ar); 6.04 (s, 4H, Ar); 5.78 (s,
H, CH). 13C-NMR (100 MHz, DMSO-d
): δ (ppm) 145.4; 142.0; 131.8; 128.6; 127.0; 124.5; 121.3. 41.3.
Calcd. For C52 12 (%) C 72.89; H 4.72; O 22.41. Found: C 73.85; H 4.67; O 21.49.
6
): δ 7.77
(
4
6
H40O
−
1
C-tetra(phenyl)pyrogallol[4]arene (chair) m.p. > 350 ˚C IR (ATR/cm ): 3300–3600 (broad), 1630, 1500,
1
1
2
464, 1368, 1282, 1247, 1209, 1064, 1015, 163, 699, 566, 416; H-NMR (400 MHz, DMSO-d
6): δ 7.86 (s,
H, OH); 7.67 (s, 2H, OH); 7.56 (s, 4H, OH); 7.45 (s, 4H, OH), 6.84 (s, 12H, Ar); 6.60 (d, J = 8 Hz, 8H,
1
3
Ar); 6.01 (s, 2H, Ar); 5.67 (s, 4H, CH); 5.20 (s, 2H, Ar). C-NMR (100 MHz, DMSO-d
6
): δ (ppm) 143.8;
41.9; 141.6; 131.8; 131.3; 128.7; 126.7; 124.2; 122.4; 121.5; 121.4; 119.8; 42.6. Calcd. For C52
2.89; H 4.72; O 22.41. Found: C 73.52; H 4.21; O 21.91.
1
7
H40O12 (%) C
Synthesis of C-tetra(phenyl)-resorcin[4]arene. A resorcinol solution (10 mmol) in 20 mL of ethanol
was added to 10 mmol of benzaldehyde, the mixture was stirred at 90 °C and 2.5 mL of concentrated
hydrochloric acid (37%) was added dropwise. The solution was refluxed for 6 h and the precipitated
solid was filtered and washed with ethanol, producing a green solid at 86% yield. The green powder
1
was dried and used for H-NMR analysis. Water was added to the ethanol used in the reaction and
washed by inducing the precipitate. The obtained solid was filtered, washed with water and was
recrystallized from acetonitrile. The second yellow solid at 14% yield was dried and used for
conformational studies.

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−
1
C-tetra(phenyl)-resorcin[4]arene(boat) m.p. > 300 ˚C IR (KBr/cm ): 3300–3600 (broad), 1600, 1470,
1
1
6
5
1
440, 1380, 1340, 1210, 1260, 1150, 850, 740, 700; H-NMR(400MHz, DMSO-d
6
): δ 8.53 (s, 8H, OH); 6.98–
.96 (m, 12H, Ar); 6.75–6.74 (m, 8H, Ar); 6.32 (br s, 4H, CH meta to OH); 6.15(s, 4H, CH orto to OH);
13
.63 (s, 4H, CH). C-NMR(100 MHz, DMSO-d ) δ (ppm): 152.4; 145.6, 130.7 ; 128.4; 126.8; 124.3; 120.5;
6
02.2; 41.6.
−1
C-tetra(phenyl)-resorcin[4]arene(chair) m.p. > 300 ˚C IR (KBr/cm ): 3300–3600 (broad), 1600, 1470,
1
1
440, 1380, 1340, 1210, 1260, 1150, 850, 740, 700; H-NMR(400MHz, DMSO-d
6
): δ 8.52 (s, 4H, OH); 8.41
(s, 4H, OH); 6,80 (s, 12H, Ar) ; 6.57 (s, 8H, Ar); 6.31 (s, 4H, Ar); 6.08 (s, 2H, Ar); 5.52 (s, 2H, Ar); 5.49
(
s, 4H, CH). 13C-NMR (100 MHz, DMSO-d
6
) δ (ppm): 152.7; 152.5; 144.7; 131.7; 129.1; 128.9; 126.9;
1
24.3; 121.0; 120.6; 101.6; 42.1.
3.2. Dynamic Studies
1
The dynamic studies were carried out by using H-NMR. The solids 1a and 2a were dissolved in
a mixture of solvents such as DMSO-d and acetonitrile (MeCN). The solution was cooled within a
6
1
range of 296.15 K to 258.15 K taking H-NMR spectra each 5 or 10 K.
4
. Conclusions
C-tetra(phenyl)-resorcin[4]arene and C-tetra(phenyl)-pyrogallol[4]arene were synthesized as
conformational mixtures composed of the boat and the chair isomers. The analysis of the
conformational mixture showed the formation of cone isomers in a greater proportion for the C-
tetra(phenyl)-resorcin[4]arene, while for C-tetra(phenyl)-pyrogallol[4]arene, the chair isomer had the
greater proportion. The dynamic studies in the solution phase showed that structures 1a and 2a are
a dynamic boat in the solution phase, in contrast with previous studies, where the structure was
reported as a cone conformer. The dynamic behavior is a consequence of absence of intramolecular
hydrogen bonds on the upper rim, as an effect of the aromatic substituent on the lower rim.
Supplementary Materials: The following are available online: Figure S1: 1H-NMR spectrum DMSO-d
6
1
conformational mixture(1a and 1b), Figure S2: IR Spectrum of tetra(phenyl)-resorcin[4]arene(1a), Figure S3: H-
NMR spectrum-DMSO-d
6
of tetra(phenyl)-resorcin[4]arene(1a), Figure S4: 13C-NMR spectrum- DMSO-d
6
of
tetra(phenyl)-resorcin[4]arene(1a), Figure S5: 2D-NMR-HSQC spectrum-DMSO-d
6
of tetra(phenyl)-
1
resorcin[4]arene(1a), Figure S6: Dynamic H-NMR study for tetra(phenyl)-resorcin[4]arene(1a), Figure S7: IR
Spectrum of tetra(phenyl)-resorcin[4]arene(1b), Figure S8: 1H-NMR spectrum-DMSO-d
6
of tetra(phenyl)-
resorcin[4]arene(1b), Figure S9: 13C-NMR spectrum of tetra(phenyl)-resorcin[4]arene (1b), Figure S10: H-NMR
1
spectra of boat(rccc)(1a), Figure S11: 1H-NMR spectrum DMSO-d
6
conformational mixture(2a and 2b) and
1
chair(rctt)(1b), Figure S12: IR Spectrum of tetra(phenyl)-pyrogallol[4]arene(2a), Figure S13: H-NMR spectrum-
DMSO-d
6
of tetra(phenyl)-pyrogallol[4]arene(2a), Figure S14: 13C-NMR spectrum-DMSO-d
of tetra(phenyl)-
6
1
pyrogallol[4]arene(2a), Figure S15: Dynamic H-NMR study for tetra(phenyl)-pyrogallol[4]arene(2a), Figure S16:
1
IR Spectrum of tetra(phenyl)-pyrogallol[4]arene(2a), Figure S17: H-NMR spectrum-DMSO-d
6
of tetra(phenyl)-
pyrogallol[4]arene(2b), Figure S18: 13C-NMR spectrum-DMSO-d
of tetra(phenyl)-pyrogallol[4]arene(2b), Figure
6
1
S19: H-NMR spectra of conformational mixture, boat(rccc)(2a) and chair(rctt)(2b) isomers.
Author Contributions: Designed the research, M.M.V.; performed the experiments and collected the data,
analyzed the results and corrected and edited the manuscript, M.M.V., J.L.C.-H. and M.Á.V.S. All authors
contributed to the preparation of the manuscript and have read and agreed to the published version of the
manuscript.
Funding: This research was funded by Department of Science, Technology and Innovation COLCIENCIAS
(Colombia). grant conv. 727.
Acknowledgments: We wish to thank the Universidad Nacional de Colombia and José Luis Casas-Hinestroza
acknowledge the Administrative Department of Science, Technology and Innovation COLCIENCIAS
(Colombia) for his Ph.D. grant conv. 727.
Conflicts of Interest: The authors declare no conflict of interest.

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Sample Availability: Samples of the compounds 1a, 2a, 1b and 2b are available from the authors.
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