Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-aminophenylboronic acid and salicylaldehyde derivatives

Article abstract of DOI:10.1016/j.ica.2013.02.033

One-pot synthesis of calixarene and hemicarcerand like compounds can be modulated by use of mono- or bis-salicylaldehyde derivatives respectively, reacting with 3-aminophenylboronic acid. Thus, the first part of this work is focused on the synthesis of calix-like compounds derived from salicylaldehyde units including different substituents on the aromatic moiety. Seven different calix structures are described and their structural analysis has been carried out by spectroscopic techniques. The second part corresponds to the description of bis-salicylaldehyde derivatives, synthesis and reactivity towards the 3-aminophenylboronic acid leading to the formation of hemicarcerand-like compounds. Aliphatic and aromatic chains were inserted as linkers between the two salicylaldehyde units in order to evaluate the influence on the formation of the hemicarcerands compounds. Both, calixarene and hemicarcerand compounds resulted from condensation reactions, wherein the formation of N-B coordination bonds plays a significant role on the macrocyclization process.

Full text of DOI:10.1016/j.ica.2013.02.033

Accepted Manuscript
Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-
aminophenylboronic acid and salicylaldehyde derivatives
Victor Barba, Paola Ramos, Danae Jiménez, Abraham Rivera, Ariel Meneses
PII:
S0020-1693(13)00073-X
http://dx.doi.org/10.1016/j.ica.2013.02.033
ICA 15352
DOI:
Reference:
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Inorganica Chimica Acta
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Revised Date:
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19 December 2012
20 February 2013
25 February 2013
Please cite this article as: V. Barba, P. Ramos, D. Jiménez, A. Rivera, A. Meneses, Calixarene and hemicarcerand-
like compounds obtained by self-assembly of 3-aminophenylboronic acid and salicylaldehyde derivatives,
Inorganica Chimica Acta (2013), doi: http://dx.doi.org/10.1016/j.ica.2013.02.033
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Calixarene and hemicarcerand-like compounds obtained by self-assembly of 3-
aminophenylboronic acid and salicylaldehyde derivatives
Victor Barba,* Paola Ramos, Danae Jiménez, Abraham Rivera and Ariel Meneses
Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av.
Universidad 1001, C.P. 62209 Cuernavaca, Morelos, México.
Abstract: One-pot synthesis of calixarene and hemicarcerand like compounds can be
modulated by use of mono- or bis-salicylaldehyde derivatives respectively, reacting with 3-
aminophenylboronic acid. Thus, the first part of this work is focused on the synthesis of
calix-like compounds derived from salicylaldehyde units including different substituents on
the aromatic moiety. Seven different calix structures are described and their structural
analysis has been carried out by spectroscopic techniques. The second part corresponds to
the description of bis-salicylaldehyde derivatives, synthesis and reactivity towards the 3-
aminophenylboronic acid leading to the formation of hemicarcerand-like compounds.
Aliphatic and aromatic chains were inserted as linkers between the two salicylaldehyde
units in order to evaluate the influence on the formation of the hemicarcerands compounds.
Both, calixarene and hemicarcerand compounds resulted from condensation reactions,
wherein the formation of N-B coordination bonds plays a significant role on the
macrocyclization process.
Keywords: Calixarenes, hemicarcerands, macrocycles, trimeric compounds, boronic acids
Corresponding author: Tel/fax +52 777 3297997
E-mail address: vbarba@uaem.mx

1. Introduction
Calixarene chemistry has received considerable attention for long time ago, and it is really
interesting to find that the large number of applications for calix-like compounds still
continues increasing [1-8]. At the beginning, calixarenes derived mainly from phenol units
were synthesized and properties as inclusion and recognition analyzed [9-12]. Nonetheless,
heteroaromatic macrocycles are more frequently part of the calix-like compounds for
several interesting reasons as: a) easy accessibility, b) rich molecular diversity, c) unique
conformation, and d) cavity modulation [13-19]. These factors make them useful
macrocycles for research in supramolecular chemistry. Thus, heterocalixaromatics with
well-defined conformations and fascinating cavity properties are powerful tools for the
construction of supramolecular arrays and frequently are used as syntons for the
construction of Metal-Organic Frameworks [20-23]. It is known that multicomponent
molecular self-assembly of heterocalixaromatics coupled with metals forms soft materials
having diverse applications in material science. Even if the synthesis of sulphur, nitrogen-
and oxygen-bridged calixarenes looks very difficult; several reports have recently appeared
describing the formidable synthetic challenges involved and denoting thus, the rapid and
tremendous development of the supramolecular chemistry of this new generation of
macrocycles [24-28].
Beside all the heterocalixarenes modifications described before, we have introduce a new
strategy to construct heterocalixarenes using nitrogen-boron coordination bonds. Thus, we
have reported that boron macrocycles having boron-nitrogen coordinative bonds are easily
formed by the reaction of salicylaldehyde derivatives and 3-aminophenylboronic acid
(Scheme 1, up) [29]. The reaction occurs in one-pot synthesis leading to the formation of
trimeric compounds in good yields. The 15-membered macrocycles are surrounded by three
aromatic units and connected by three N-B coordinative bonds having a cone-cone
conformation, relating these with a calix-like form. These boroncalix[3]arenes have been
found to be useful for molecular encapsulation of neutral molecules, amines and
ammonium salts [30].

By the way, using hydroxyketones instead of salicylaldehyde derivatives the macrocyclic
compounds are also obtained but having a partial-cone conformation which is not useful
for recognition process [31]. It is important to remark that during the reaction, an
alcoholysis reaction occurs forming the ester group depending of the alcohol used, the
alcohoxy group is oriented always outside from the macrocycle. In fact in alcohol absence,
the condensation reaction takes place between two B-OH units forming B-O-B bridges
joining two calixarene units [32].
In another hand, bis-calixarenes can be obtained also in one pot synthesis from bis-
salicylaldehyde derivatives with 3-aminophenylboronic acid in moderate yields (Scheme 1,
down) [33]. In these cases the N-B coordination bond, the imine group formation and the
alcoholysis reaction, are the main factors responsible for the macrocyclization pathway. In
a previous report, a CH2 group connects the two salicylaldehyde units leading to
hemicarcerand-like compounds in good yields. The X-ray analysis reveals the inclusion of
two benzene molecules in its cavity, given evidence that these compounds acts as molecular
containers.
The principal topics in the construction of macrocycles based on boronic esters are: a)
modify the ring size, b) change the conformational flexibility and c) increase the thermal
stability. It is know that these factors are relevant in the formation on new Covalent
Organic Frameworks which are convenient for potential applications as porous materials
[34-37]. Herein, we describe the synthesis and characterization of calix- and
hemicarcerand-like compounds in order to determine additional structural factors that have
influence in their formation. The synthesis was done from salicylaldehyde derivatives and
3-aminophenylboronic acid. In the first part, the preparation of boroncalixarenes is
described and later, the formation of hemicarcerands is discussed. In all cases, compounds
were analyzed using techniques as infrared, nuclear magnetic resonance, mass spectrometry
and elemental analysis in order to get a complete characterization.

2. Results and discussion
In order to expand the number of molecular receptors type boroncalix[3]arenes, herein we
have synthesized the trimeric boron compounds 1-4. The direct reaction between the 5-
bromo-, 5-methyl or 4-(diethylamine) salicylaldehyde derivatives with 3-
aminophenylboronic acid (Scheme 2), offers the new calix-like compounds in moderate
yields, stables under moisture to room temperature and having high melting points (>260
C). Compounds 1-3 were obtained using methanol as solvent leading to the boron esters
having the OMe group attached to the boron atom, in case of compound 4 ethanol was used
as solvent leading to an ethoxy group joined to the boron atom. As describe in our previous
reports [32], the use of different alcohols during the reaction change the alcohoxy group
attached to the boron atom, changing thus the physico-chemical properties; for instance
larger chains leads to increase solubility in less polar solvents.
In all four cases, the IR spectra showed a band in the range of 1617 - 1632 cm-1, assigned to
the stretching of the v(C=N) group indicating the presence of the imine group. The
macrocyclic nature of the derivatives was suggested by mass spectrometry, a FAB+ analysis
reveals that the highest peak corresponds to the trimeric molecular ion, except for
compound 1 wherein the observed peak corresponds to the loss of a methoxy group from a
trimeric compound [M-OMe]+, actually these peak has been identify as a characteristic
pattern in analogous calix-like derivatives [30].
The NMR spectra for 1-4 showed signals for only a third part of the molecule, indicating
the C3 symmetric nature which is characteristic for a cone-cone conformation for this type
of molecules [30,32]. The 1H spectra showed a single signal to down fields (8.20-8.80 ppm)
while the 13C spectra shown a single signal in the range of 161.4-163.3 ppm, denoting thus
the formation of the HC=N moiety. The chemical shift of the hydrogen atoms
corresponding to the MeO group are shifted at 3.16 to 3.40 ppm, the corresponding signals
in 13C for the same group were found at 45.3 - 48.0 ppm. By the way, for compound 4 the
1
13
EtO moiety showed signals at H in 3.56 (q) and 1.18 (t) ppm, whereas in C spectra
signals at 48.0 and 15.6 ppm were observed. The 11B NMR confirms the tetrahedral
character of the boron atoms having chemical shifts at 2.0-4.5 ppm as observed for
analogous compounds [30,32].

As mention above, boroncalixarenes have been used to trap neutral guest [30] and thus, in
order to increase the hydrophobic nature of the cavity for the calix-like compounds, the 2-
hydroxynaphtaldehyde was used for the condensation with the 3-aminophenylboronic acid
in ethanol leading to the formation of compound 5 (Scheme 3). It was obtained in good
yield but the solubility decreased with respect to its parent compounds 1-4 in all common
organic solvents, in fact making the reaction under methanol, a highly insoluble yellow
solid is obtained in good yield. For compound 5, the mass spectra gave evidence for the
trimeric product formation, a peak at m/z = 903 was observed which corresponds to the
molecular ion, additionally, the peak at m/z = 858 reveals the loss of an EtO moiety. The IR
shows the characteristic band for the imine group at 1625 cm-1 and the 1H spectrum showed
a single signal at 8.91 ppm assigned to the proton of the iminic group. In the 13C spectrum a
single signal at 163.7 ppm was observed assigned to the same group. The 11B chemical shift
was observed at 5 ppm denoting the tetrahedral character for the boron atom.
One of the main problems to use these compounds as molecular receptors is the low
solubility, even in water for possible biological applications. So, in order to increase the
hydrophilic character surrounded the calix structure, we decide to introduce phosphate
groups in the periphery of the macrocycle. Thus, the condensation reaction was done using
pyridoxal 5’-phosphate with the boronic acid. Under methanol reflux compound 6 is
obtained whereas using ethanol as solvent it is possible to isolate the compound 7 (Scheme
3). In both cases the presence of the phosphate at the periphery of the upper rim, introduce
a high solubility in polar solvents as alcohols or water. Actually, all the previous
boroncalix-like compounds described are insoluble in water. This characteristic could help
us to expand the analysis of these systems as molecular receptors in biological systems.
Nevertheless, as a consequence of the OH groups presents at the pyridoxal which are
susceptible for condensation reactions, the yields for the trimeric compounds formation are
relatively lower compared with 1-5 (23 and 28 % for 6 and 7, respectively). Additionally, a
white insoluble solid is isolated as byproduct in both cases, perhaps being part of a
polymeric chain which was impossible to characterize. Mass spectrometry analysis
confirms the trimeric nature for these derivatives. The IR spectra show bands at 1642 and
1631 cm-1 for 6 and 7, respectively. The 1H NMR showed that the imine proton is shifted to
lower fields in comparison with the analogous compounds, a single signal was observed at

9.27 in both cases, the corresponding signal at 13C spectra was observed at 160.1 and 160.2
ppm, for 6 and 7, respectively. 31P NMR spectra of these calixarenes including the
phosphate groups showed a broad signal at ꢀ: 6.6 and 6.5 ppm respectively, which are in
accordance with the records reported for compounds having this group [38].
Following the strategy described at Scheme 1 for the construction of the hemicarcerands, at
the beginning the synthesis of bis-salicylaldehyde derivatives was carried out. Ligand 8 was
produced from the 5-methylsalicylaldehyde and formaldehyde in acetic acid in very little
yield (9.6%) [39]. The new ligand possess a methylene moiety connecting the two
salicylaldehyde units at position 3. The ligand 8 was allowed to react with 3-
aminophenylboronic acid to get the macrocyclic structure 12. As expected, 3 equivalents of
ligand 8 reacts with 6 equivalents of the boron acid to give a trimeric compound (Scheme
4), in a similar way that the observed using a similar ligand having the methylene unit at
position 5 [33]. The product is very little soluble in common organic solvents and was
obtained in moderate yield (68%). The IR shows the stretching band v(C=N) at 1625 cm-1
which is shifted to lower wavenumber in comparison with the stretching band for the
carbonyl group of the ligand (1645 cm-1). Mass spectrometry reveals the macrocyclic
structure showing a peak corresponding to the molecular ion with the loss of an OMe
group, as observed for related compounds. The high symmetry for this molecule was notice
from the 1H, 13C and 11B NMR spectra, in all three cases only a six part of the molecule was
noticed. By NMR it was possible identify the iminic group, in 1H the chemical shift for the
hydrogen atom was observed as single signal at 8.19 ppm, whereas in 13C, the
corresponding carbon atom showed the signal at 163.5 ppm. The methanolysis reaction also
was evidenced since the observation of signals at 3.36 ppm and 38.2 ppm from proton and
11
carbon spectra, respectively. The B spectrum shows a broad signal at 1.0 ppm giving
evidence for the tetrahedral character of the boron atom.
In addition, large alkyl chains separating the two salicylaldehyde units where introduced in
order to increase the size of the cavity for the hemicarcerand-like derivatives. Therefore,
the ligands 9-11 were synthesized using 2,4-dihydroxybenzaldehyde and the corresponding
alkyl dibromide (1,2-dibromoethane, 1,3-dibromopropane and ꢁ,ꢁ’-dibromo-p-xylene).
The reaction was carried out under reflux using KHCO3 as base in accordance to a method

previously reported [40]. These compounds were obtained in low yields (6, 10 and 12 %)
mainly because of the presence of two hydroxyl groups in the aromatic ring giving little
selectivity to form the required compounds, additionally a solid white was obtained which
was difficult to characterize. In all three cases the ligands were characterized by 1H and 13C
NMR as well as IR and mass spectrometry. For instance, from the mass spectra, the
observed peaks at m/z= 302, 316 and 378 corresponds to the molecular ion for compounds
9-11 confirming the formation of the products. In addition, for compound 10 in was
possible to get suitable crystals for the X-ray analysis [41], the molecular structure is
showed at Figure 1 wherein the alternate conformation between the carbonyl groups is
observed. This conformation is very important in the formation of the hemicarcerand- like
compounds [33]. At the supramolecular level, the molecules are ordered in a zig-zag
conformation leading to extended sheets (Figure 2).
The ligands 9-11 were allowed to react with the 3-aminophenylboronic acid in order to get
macrocyclic hemicarcerand-like compounds (Scheme 5). The reactions were done using
ethanol as solvent for 13 and 14, and methanol for 15. It is noteworthy to remark that using
methanol for 13 and 14, and ethanol for 15, the reaction leads to the formation of insoluble
white solids having high melting points (> 360 °C). First evidence of the macrocyclic
structure formation was provide by the mass spectrometry, wherein for compounds 13 and
14 the peak corresponding to the molecular ion was observed at m/z= 1681 and 1723,
respectively. The Figure 3 shows part of the FAB-MS spectrum for compound 14,
indicating that the isotopic pattern correlated with the calculated. Moreover, in all three
cases the corresponding peak characteristic for the loss of an OR group was observed at m/z
= 1636 (M-OEt), 1677 (M-OEt) and 1794 (M-OMe) for 13, 14 and 15 respectively. In the
IR analysis, the presence of the stretching band v(C=N) at 1622, 1618 and 1621 cm-1
confirmed the imine group formation. These molecules have high symmetry as noticed
from the NMR spectra, signals corresponding to only a sixth part of the whole molecule
were observed. For instance, at 1H a single signal at 8.88, 8.89 and 8.87 ppm was observed
for the iminic hydrogen of 13, 14 and 15, respectively. The chemical shift of the 13C for the
11
same group was observed at 163.9 for compounds 13 and 15 and B chemical shift was
registered at 1.0 and 2.0 ppm for 13 and 15, respectively. Compound 14 was very little
13
11
soluble and was impossible to get the C and B NMR spectra. Unfortunately, we were

unable to get crystals suitable for the X-ray diffraction analysis; therefore a mechanical
molecular model was used at the MM+ level of theory [42] for compounds 13, 14 and 15 in
order to have an idea of the whole geometry for this type of complexes (Figure 4). From
there, it was noticed that the presence of large linkers change the whole structure
conformation reducing the cavity size, and at the same time reducing the possibility for
host-guest possible applications.
3. Conclusions
We have carried out the formation of boroncalix[3]arenes having different physical
properties by changing the functional groups of the salicylaldehyde moiety. For instance,
the introduction on the naphthalene moiety gives more hydrophobic effect, while the
presence of phosphate fragments leads to give a higher hydrophilic behavior. By the way,
the formation of hemicarcerand-like compounds was also done, wherein the insertion of
short or large aliphatic fragments connecting two salicylaldehyde moieties have not
influence on the hemicarcerand like compounds formation but in the whole geometry as
observed from the mechanical molecular model. Further investigations as molecular
containers for neutral molecules are current in our lab.
4. Experimental part
4.1. Materials
All reagents and solvents were acquired from commercial suppliers and used without
further purification.
4.2. Instrumentation
The 1H, 13C and 119Sn NMR spectra were recorded at room temperature using a Varian Unit
400 spectrophotometer. As standard references were used TMS (internal, 1H, ꢀ = 0.00 ppm,
13C, ꢀ = 0.0 ppm) and BF3.Et2O (external, 11B, ꢀ = 0.0 ppm). The 2D COSY and HETCOR
1
experiments have been carried out for the unambiguous assignment of the H and 13C

signals present at the NMR spectra. Infrared spectra have been recorded on a Bruker Vector
22 FT-IR spectrophotometer. Mass spectra were obtained with Jeol JMS 700 equipment.
Melting points were determined with a Büchi B-540 digital apparatus.
4.3. X-ray crystal-structure determination
X-ray diffraction studies for compound 10 were performed on a Bruker-APEX
diffractometer with a CCD area detector, using Mo Kα-radiation, (λ= 0.71073 Å) and a
graphite monochromator. Frames were collected at T = 293 K. The measured intensities
were reduced to F2. Structure solution, refinement and data output were carried out with the
SHELXTL-NT program package [43]. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were placed in geometrically calculated positions using a
riding model.
4.4. General method for the preparation of calix-like complexes 1-7
Compounds 1-7 were synthesized from the equimolecular reaction of the corresponding
salicylaldehyde derivative with 3-aminophenylboronic acid monohydrate using 10 mL of
benzene as solvent and 2 mL of the corresponding alcohol (methanol or ethanol). The
reaction mixtures were stirred for 4 h under reflux. After that, part of the solvent and the
water formed through the triple condensation reaction were removed using a Dean-Stark
trap. The final products were recovered by filtration and purified by recrystallization in a
solvent mixture MeOH/CHCl3 (1:3 ratio).
Compound 1 was prepared from 0.30 g (1.93 mmol) of 3-aminophenylboronic acid
monohydrate and 0.38 g (1.92 mmol) 5-bromosalicylaldehyde in 10 mL of benzene and 10
mL of methanol. The product was obtained as a yellow powder. Yield: 0.52 g (85%);
-1
v
m.p.decomp > 300 °C. IR (KBr) (cm ): 3547 (m), 3055 (w), 2819 (w), 1625 (C=N, s),
1547 (s), 1474 (s), 1371 (m), 1299 (m), 1202 (m), 1120 (w), 944 (w), 877 (w), 824 (w), 706
(w), 561 (w). EI-MS m/z (%): 917 ([M+-OMe], 13), 619 (15), 481 (55), 453 (25), 379 (87),
378 (35), 257 (22), 241 (100), 167 (24), 139 (35), 104 (51), 79 (47), 41 (38). 1H NMR (400

MHz, DMSO-d6) ꢀ: 8.20 (3H, s, H-7), 7.89 (3H, d, J = 2.6, H-6), 7.78 (3H, s, H-9), 7.75-
7.73 (3H, m, H-12), 7.55 (3H, dd, J = 7.4, 2.6 Hz, H-4), 7.45 (3H, d, J = 7.4 Hz, H-13),
7.44 (3H, d, J = 2.2 Hz, H-11), 6.95 (3H, d, J = 7.4 Hz, H-3), 3.35 (9H, s, CH3O) ppm. 13C
NMR (100 MHz, DMSO-d6) ꢀ: 161.4 (C-7), 159.2 (C-2), 146.8 (C-8), 135.3 (C-4), 133.8
(C-6), 133.0 (C-12), 128.5 (C-11), 127.0 (C-9), 122.7 (C-13), 121.1 (C-1), 119.0 (C-3),
11
109.8 (C-5), 45.3 (CH3O) ppm. B NMR (64 MHz, DMSO-d6) ꢀ: 2.0 ppm (h1/2 = 2400
Hz). Elemental Anal. Calc. for C42H33B3N3Br3O6: C 53.21, H 3.50, N 4.43 %. Found: C
52.99, H 3.37, N 4.25 %.
Compound 2 was prepared from 0.30 g (1.93 mmol) of 3-aminophenylboronic acid
monohydrate and 0.26 g (1.91 mmol) 5-methylsalicylaldehyde in 30 mL of benzene and 3
mL of methanol. The product was obtained as a yellow powder. Yield: 0.24 g (54%); m.p.=
-1
v
298-300 °C. IR (KBr) (cm ): 3434 (m), 2920 (m), 1632 (C=N, s), 1562 (s), 1487 (m),
1382 (s), 1294 (m), 1220 (w), 1161 (w), 1082 (w), 983 (w), 951 (w), 884 (w), 821 (w), 786
(w), 567 (w). FAB+-MS m/z (%):753 ([M+H]+, 15), 712(34), 691 (25), 690 (15), 677 (15),
592 (15), 471 (25), 457 (17), 307 (56), 264 (100), 263 (30), 220 (13). 1H NMR (400 MHz,
DMSO-d6) ꢀ: 8.80 (3H, s, H-7), 7.77 (3H, s, H-9), 7.72 (3H, d, J = 2 Hz, H-6), 7.45 (3H, t,
J = 6.8 Hz, H-12), 7.45 (3H, dt, J = 6.8 Hz, 1.6, H-13), 7.43 (3H, dt, J = 6.8 Hz, 1.6, H-11),
7.23 (3H, dd, J = 8.4, 2.0 Hz, H-4), 6.87 (3H, d, J = 8.4 Hz, H-3), 3.40 (9H, s, CH3O), 2.28
13
(9H, s, CH3arom) ppm. C NMR (100 MHz, DMSO-d6) ꢀ: 162.8 (C-7), 158.0 (C-2), 147.3
(C-8), 133.9 (C-4), 132.6 (C-6), 132.1 (C-12), 128.5 (C-11), 127.6 (C-5), 127.0 (C-9),
122.6 (C-13), 119.0 (C-1), 116.4 (C-3), 46.00 (CH3O), 20.0 (CH3arom). 11B NMR (64 MHz,
DMSO-d6) ꢀ: 2 ppm (h1/2 = 2181 Hz). Elemental Anal. Calc. for C45H42B3N3O6: C 71.75, H
5.62, N 5.57 %. Found: C 71.49, H 5.58, N 5.45 %.
Compound 3 was prepared from 0.37 g (2.41 mmol) of 3-aminophenylboronic acid
monohydrate and 0.46 g (2.41 mmol) 4-diethylamine salicylaldehyde in 50 mL of benzene
and 50 mL of methanol. The product was obtained as a yellow powder. Yield: 0.63 g
-1
v
(85%); m.p. = 260-262 °C. IR (KBr) (cm ): 3365 (m), 2973 (C-H, m), 1705 (w), 1618
(C=N, s), 1510 (s), 1445 (s), 1409 (s), 1350 (s), 1222 (s), 1141 (s), 1076 (m), 1009 (m), 932
(m), 709 (w), 526 (w). FAB+-MS m/z (%): 924 ([M]+, 12), 909 (25), 893 ([M-MeO]+, 100),
1
879 (95), 878 (59), 865 (35), 849 (20), 835 (12), 819 (8). H NMR (200 MHz, DMSO-d6)

ꢀ: 8.68 (3H, s, H-7), 7.69 (3H, s, H-3), 7.62 (3H, d, J = 7.3 Hz, H-13), 7.35 (3H, t, J = 7.3
Hz, H-12), 6.96 (3H, d, J = 7.2 Hz, H-6), 6.59 (3H, dd, J = 7.2, 2.0 Hz, H-5), 6.32 (3H, d, J
= 7.3 Hz, H-11), 6.06 (3H, s, H-9), 3.40 (12H, q, J = 4.0 Hz, -CH2N), 3.16 (9H, s, CH3O),
13
1.11 (18H, t, J = 4.0 Hz, CH3CH2N) ppm. C NMR (50 MHz, DMSO-d6) ꢀ: 162.3 (C-7),
161.5 (C-2), 153.3 (C-4), 147.1 (C-8), 132.1 (C-13), 129.3 (C-12), 128.9 (C-6), 127.2 (3),
116.1 (C-5), 108.0 (C-1), 104.5 (C-11), 98.3 (C-9), 48.0 (CH3O), 44.4 (-CH2N), 13.8
(CH3CH2N). 11B NMR (64 MHz, DMSO-d6) ꢀ: 3.6 ppm (h1/2 = 1453 Hz). Elemental Anal.
Calc. for C54H63B3N6O6: C 70.15, H 6.86, N 10.38 %. Found: C 70.06, H 6.67, N 10.24 %.
Compound 4 was prepared from 0.37 g (2.41 mmol) of 3-aminophenylboronic acid
monohydrate and 0.46 g (2.41 mmol) 4-diethylamine salicylaldehyde in 50 mL of benzene
and 50 mL of ethanol. The product was obtained as a yellow powder. Yield: 0.67 g (87%);
-1
v
m.p.= 282-285 °C. IR (KBr) (cm ): 3428 (w), 2971 (w), 1617 (C=N, s), 1511 (s), 1445
(m), 1409 (m), 1349 (m), 1238 (m), 1140 (m), 1076 (w), 1011 (w), 1004 (m), 967 (w), 789
(w), 709 (w). FAB+-MS m/z (%): 966 ([M]+, 8), 938 (10), 922 ([M-EtO]+, 100) 894 (22),
1
893 (41), 865 (27), 864 (21), 848 (10), 835 (6), 819 (6), 818 (5). H NMR (200 MHz,
DMSO-d6) ꢀ: 8.72 (3H, s, H-7), 7.67 (3H, s, H-3), 7.61 (3H, d, J = 7.2 Hz, H-13), 7.27
(3H, t, J = 7.2 Hz, H-12), 6.87 (3H, d, J = 6.8 Hz, H-6), 6.58 (3H, d, J = 6.8 Hz, H-5), 6.39
(3H, d, J = 7.2 Hz, H-11), 6.01 (3H, s, H-9), 3.56 (6H, q, J = 5.6 Hz, CH3CH2O), 3.33
(12H, q, J = 4.7 Hz, CH3CH2N), 1.18 (9H, t, J = 5.6 Hz, CH3CH2O), 1.09 (18H, t, J = 4.7
13
Hz, CH3CH2N) ppm. C NMR (100 MHz, DMSO-d6) ꢀ: 163.3 (C-7), 161.1 (C-2), 152.1
(C-4), 147.0 (C-8), 132.4 (C-13), 128.1 (C-12), 128.7 (C-6), 126.9 (3), 116.3 (C-5), 107.8
(C-1), 104.2 (C-11), 99.3 (C-9), 48.0 (CH3CH2O), 45.2 (CH3CH2N), 15.6 (CH3CH2O), 14.7
(CH3CH2N). 11B NMR (64 MHz, DMSO-d6) ꢀ: 4.5 ppm (h1/2 = 2367 Hz). Elemental Anal.
Calc. for C57H69B3N6O6: C 70.82, H 7.19, N 8.69 %. Found: C 70.71, H 7.11, N 8.49 %.
Compound 5 was prepared from 0.37 g (2.12 mmol) of 3-aminophenylboronic acid
monohydrate and 0.36 g (2.12 mmol) 2-hydroxynaphtaldehyde in 50 mL of benzene and 50
mL of ethanol. The product was obtained as a yellow powder. Yield: 0.51 g (80%); m.p.=
-1
v
380-383 °C. IR (KBr) (cm ): 3429 (w), 2969 (C-H, w), 1625 ( C=N, s), 1548 (s), 1460
(s), 1401 (m), 1345 (m), 1239 (m), 1062 (m), 1004 (m), 954 (m), 861 (m), 793 (w), 679
(m). FAB+-MS m/z (%): 903 ([M]+, 5), 858 ([M-CH3CH2O]+, 10), 829 (2), 562 (1), 307

1
(17), 289 (10), 154 (100), 136 (73), 90 (23), 78 (18). H NMR (200 MHz, DMSO-d6) ꢀ:
8.91 (3H, s, H-C=N), 7.94-7.02 (24H, m, Harom), 3.62 (6H, q, J = 4.2 Hz, CH2), 1.16 (9H, t, J
13
= 4.2 Hz, CH3) ppm. C NMR (50 MHz, DMSO-d6) ꢀ: 163.7 (CC=N), 158.7 (Carom-O),
146.2, 135.1, 132.4, 132.2, 130.1, 129.1, 128.0, 126.8, 126.6, 123.9, 123.7, 122.3, 121.5
(Carom), 46.1 (CH2), 14.7 (CH3). 11B NMR (64 MHz, DMSO-d6)ꢀ: 5 ppm (h1/2 = 2486 Hz).
Elemental Anal. Calc. for C57H48B3N3O6: C 75.77, H 5.35, N 4.65 %. Found: C 75.56, H
5.27, N 4.58 %.
Compound 6 was prepared from 0.125 g (0.8066 mmol) of 3-aminophenylboronic acid
monohydrate and 0.20 g (0.8092 mmol) pyridoxal 5’-phosphate hydrate in 3 mL of benzene
and 30 mL of methanol. The product was obtained as a yellow powder. Yield: 0.07 g (23
-1
v
%); m.p.decomp = 210 °C. IR (KBr) (cm ): 3442(s), 20741(w), 1642(C=N, s), 1387(m),
1249(m), 1034(w), 926(w), 698(w), 503(m). FAB+-MS m/z (%): 1037 ([M -OMe, -H2O]+,
1
2), 934(1), 807(4), 646(26), 645(9), 332(7), 202(100). H NMR (400 MHz, DMSO-d6) ꢀ:
9.27 (3H, s, H-7), 8.10 (3H, s, H-4), 7.96 (3H,s, H-9), 7.77 (3H, d, J = 7.6 Hz, H-13), 7.62
(3H, d, J = 7.6 Hz, H-11), 7.47 (3H, t, J = 7.6 Hz, H-12), 5.55 (6H, br, OH), 5.18 (6H, d, J
13
= 7.2 Hz, H-6), 2.45 (9H, s, CH3O), 2.08 (9H, s, CH3arom) ppm. C NMR (100 MHz,
DMSO-d6) ꢀ: 160.1 (C-7), 153.5 (C-2), 149.6 (C-4), 145.8 (C-3), 138.5 (C-8), 134.0 (C-5),
129.3 (C-9), 128.8 (C-11), 128.2 (C-12), 122.6 (C-13), 120.1 (C-1), 62.2 (C-6), 38.3
11
(CH3O), 18.7 (CH3arom) ppm; B NMR (64 MHz, DMSO-d6) ꢀ: 1.0 ppm (h1/2= 2008 Hz).
31P NMR (162 MHz , DMSO-d6) ꢀ: - 6.6 ppm. Elemental Anal. Calc. for C45H46B3N6P3O18:
C 49.84, H 4.27, N 7.75 %. Found: C 49.86, H 4.17, N 7.64 %.
Compound 7 was prepared from 0.125 g (0.8066 mmol) of 3-aminophenylboronic acid
monohydrate and 0.20 g (0.8092 mmol) pyridoxal 5’-phosphate hydrate in 3 mL of benzene
and 30 mL of ethanol. The product was obtained as a yellow powder. Yield: 0.08 g (28 %);
-1
v
m.p.
= 240 °C. IR (KBr) (cm ): 3455(s), 2927(w), 1631(C=N, s), 1391(m),
decomp
1166(w), 1027(w), 699(w), 504(m); FAB+-MS m/z (%): 1128 ([M]+, 5), 1014(5), 915(5),
810(5), 758(10), 643(10), 615(5), 524(10), 460(5), 391(20), 307(100), 289(70), 219(50). 1H
NMR (400 MHz, DMSO-d6) ꢀ: 9.27 (3H, s, H-7), 8.05 (3H, s, H-4), 7.95 (3H, s, H-9), 7.78
(3H, d, J= 7.2 Hz, H-13), 7.63 (3H, dt, J=7.2 Hz, 1.2 Hz, H-11), 7.48 (3H, t, J=7.6 Hz, H-
12), 5.20 (6H, d, J=6.8 Hz, H-6), 3.50 (6H, br, OH), 3.43 (6H, q, J= 7 Hz, CH3CH2O), 2.46

(9H, S, CH3arom), 1.04 (9H, t, J= 7 Hz, CH3CH2O) ppm. 13C NMR (100 MHz, DMSO-d6) ꢀ:
160.2 (C-7), 153.3 (C-2), 149.5 (C-4), 145.9 (C-3), 138.8 (C-8), 133.8 (C-5), 129.0 (C-9),
128.7 (C-11), 128.2 (C-12), 127.8 (C-10), 122.5 (C-13), 119.8 (C-1), 62.1 (C-6), 38.9
11
(CH3CH2O), 18.9 (CH3arom), 14.8 (CH3CH2O) ppm; B NMR (64 MHz, DMSO-d6) ꢀ: 3.5
ppm (h1/2= 2106 Hz). 31P NMR (162 MHz , DMSO-d6) ꢀ: - 6.5 ppm. Elemental Anal. Calc.
for C48H54B3N6P3O18: C 51.09, H 4.82, N 7.44 %. Found: C 51.06, H 4.71, N 7.58 %.
4.5. Preparative method for ligands 8-11
Ligand 8 was prepared following a synthetic method described before [39] from 1.00 g of
2-hydroxy-5-methylbenzaldehyde and 0.44 g of p-formaldehyde using 25 mL of acetic acid
-1
v
and 3 drops of sulfuric acid. Yield 9.6% (0.13g), m.p. = 150-153 °C. IR (KBr) (cm ):
3429 (w), 2919 (w), 1645 (C=O, s), 1457 (m), 1382 (m), 1329 (m), 1301 (m), 1265 (m),
1218 (m), 1164 (w), 1035 (w), 991 (w), 739 (w), 715 (w), 598 (w). EI-MS m/z (%): 284
([M]+, 100), 256 (12), 237 (25), 208 (28), 165 (34), 149 (76), 120 (70), 91 (54), 77 (28), 65
(13). 1H NMR (400 MHz, CDCl3) ꢀ: 11.08 (2H, s, OH), 9.76 (2H, s, H-7), 7.22 (2H, d, J =
1.8 Hz, H-6), 7.14 (2H, d, J = 1.8 Hz, H-4), 3.91 (2H, s, H-8), 2.22 (6H, s, CH3) ppm.
13C NMR (100 MHz, CDCl3) ꢀ: 196.8 (C-7), 157.2 (C-2), 139.3 (C-6), 131.9 (C-4), 129.0
(C-3), 128.6 (C-5), 120.5 (C-1), 28.1 (C-8), 20.5 (CH3) ppm. Elemental Anal. Calc. for
C17H16O4: C 71.75, H 5.62 %. Found: C 70.92, H 5.60 %.
Ligands 9-11 were synthesized according to the reported method [40] from two equivalents
of 2,4-dihydroxybenzaldehyde, one equivalent of the corresponding dibromoalkyl
derivative and two equivalents of KHCO3 using acetone as solvent. After 72 h under reflux,
the mixture was filtered and the product was extracted from the solid washing twice with
CH2Cl2, evaporation of the solvent allows isolate the pure compounds.
Compound 9 was prepared from 1.00 g (7.24 mmol) of 2,4-dihydroxybenzaldehyde and
0.68 g (3.62 mmol) of 1,2-dibromoethane in 50 mL of acetone. The product was obtained
-1
v
as a white powder. Yield: 0.06 g (6 %); m.p. = 165-169 °C. IR (KBr) (cm ): 3423 (m),
2930 (m), 2864 (m), 1728 (s), 1638 (C=O, s), 1469 (m), 1376 (m), 1333 (m), 1285 (s),
1124 (m), 1074 (w), 1034 (w), 969 (w), 747 (m), 629 (m). EI-MS m/z (%): 302 (M+, 100),

1
164 (46), 150 (23), 137 (25), 136 (20), 111 (15), 110 (9), 65 (15). H NMR (200 MHz,
CDCl3) ꢀ: 11.42 (2H, s, OH), 9.67 (2H, s, H-7), 7.39 (2H, d, J = 7.6 Hz, H-6), 6.52 (2H, dd,
J = 7.6, 2.4 Hz, H-5), 6.40 (2H, d, J = 2.4 Hz, H-3), 4.32 (4H, s, CH2) ppm. 13C NMR (50
MHz, CDCl3) ꢀ: 194.6 (C-7), 165.6 (C-4), 164.6 (C-2), 135.5 (C-6), 115.7 (C-1), 108.9 (C-
5), 101.5 (C-3), 66.7 (CH2) ppm. Elemental Anal. Calc. for C16H14O6: C 63.57, H 4.66 %.
Found: C 63.52, H 4.62 %.
Compound 10 was prepared from 0.96 g (6.96 mmol) of 2,4-dihydroxybenzaldehyde and
0.70 g (3.48 mmol) of 1,3-dibromopropane in 50 mL of acetone. The product was obtained
-1
v
as a white powder. Yield: 0.11 g (10 %); m.p. = 117-120 °C. IR (KBr) (cm ): 3405 (m),
2947 (w), 2881(w), 1634 (C=O, s), 1506 (w), 1464 (w), 1374 (m), 1331 (m), 1225 (s), 1183
(m), 1117 (m), 1046 (m), 989 (m), 763 (w), 631 (w). EI-MS m/z (%): 316 (M+, 9), 151 (5),
87 (9), 71(100), 43 (26). 1H NMR (400 MHz, CDCl3) ꢀ: 11.40 (2H, s, OH), 9.65 (2H, s, H-
7), 7.37 (2H, d, J = 7.7 Hz, H-6), 6.47 (2H, dd, J = 7.7, 2.2 Hz, H-5), 6.37 (2H, d, J = 2.2
13
Hz, H-3), 4.14 (4H, t, J = 6.0 Hz, OCH2), 2.24 (2H, qn, J = 6.0 Hz, OCH2CH2) ppm. C
NMR (50 MHz, CDCl3) ꢀ: 194.5 (C-7), 166.0 (C-4), 165.0 (C-2), 135.5 (C-6), 115.9 (C-1),
108.8 (C-5), 101.4 (C-3), 64.8 (OCH2), 29.8 (OCH2CH2) ppm. Elemental Anal. Calc. for
C17H16O6: C 64.55, H 5.09 %. Found: C 64.49, H 4.92 %.
Compound 11 was prepared from 1.11 g (8.03 mmol) of 2,4-dihydroxybenzaldehyde and
1.06 g (4.01 mmol) of ꢁ,ꢁ’-dibromo-p-xilene in 50 mL of acetone. The product was
-1
v
obtained as a white powder. Yield: 0.18 g (12 %); m.p. = 195-199 °C. IR (KBr) (cm ):
3446 (m), 2951 (w), 2865 (w), 1738 (m), 1639 (C=O, s), 1506 (m), 1378 (m), 1223 (s),
1179(m), 1117 (m), 1000 (m), 810 (m), 628 (w), 547 (w). EI-MS m/z (%): 378 (M+, 18)
1
293 (5), 241(100), 143 (10), 104 (60), 69 (8). H NMR (400 MHz, DMSO-d6) ꢀ: 10.01
(2H, s, H-7), 7.62 (2H, d, J = 7.6 Hz, H-6), 7.48 (4H, s, CHarom), 6.63 (2H, dd, J = 7.6, 2.4
13
Hz, H-5), 6.55 (2H, d, J = 2.4, H-3), 5.19 (4H, s, CH2), 3.26 (2H, s, OH) ppm. C NMR
(100 MHz, DMSO-d6) ꢀ: 190.8 (C-7), 164.7 (C-4), 163.0 (C-2), 136.0 (CCH2), 132.0 (C-6),
127.9 (CHarom), 116.3 (C-1), 107.8 (C-5), 101.7 (C-3), 69.3 (CH2) ppm. Elemental Anal.
Calc. for C22H18O6: C 69.83, H 4.79 %. Found: C 69.69, H 4.67 %.

4.6. General method for the preparation of hemicarcerand complexes 12-15
Compounds 12-15 were synthesized by reacting 3-aminophenylboronic acid monohydrate
with the corresponding bis-salicylaldehyde derivative (2:1 ratio) using a mixture of 5 mL of
benzene and 20 mL of the corresponding alcohol (methanol or ethanol) as solvent. The
reaction mixtures were stirred for 4 h under reflux. After that, part of the solvent and the
water formed through the triple condensation reaction were removed using a Dean-Stark
trap. The final products were recovered by filtration and purified by washing with the same
alcohol used for the reaction.
Compound 12 was prepared from 0.027 g (0.18 mmol) of 3-aminophenylboronic acid
monohydrate and 0.030 g (0.09 mmol) of ligand 8 in methanol. The product was obtained
-1
v
as a yellow powder. Yield: 0.043 g (68 %); m.p. decomp = 300 °C. IR (KBr) (cm ): 3427
(w), 2921 (w), 1625 (C=N, s), 1564 (s), 1459 (m), 1416 (m), 1368 (m), 1319 (m), 1221 (m),
1168 (w), 1104 (w), 986 (w), 898 (w), 789 (w), 679 (w), 563 (w). FAB+-MS m/z (%): 1511
([M-OMe]+, 7), 1422 (2), 1322 (2), 1222 (2), 1063 (2), 870 (2), 766 (2), 613 (4), 460 (16),
1
390 (8), 307 (100), 289 (60), 161 (32). H NMR (200 MHz, DMSO-d6) ꢀ: 8.19 (6H, H-7),
7.81 (6H, s, H-9), 7.77 - 7.70 (6H, m, H-12), 7.46 (6H, d, J = 6.6 Hz, H-13), 7.36 (6H, d, J
= 6.6 Hz, H-11), 7.31 (6H, s, H-6), 7.08 (6H, s, H-4), 3.96 (6H, s, CH2), 3.36 (18H, s,
CH3O), 2.23 (18H, s, CH3arom) ppm. 13C NMR (50 MHz, DMSO-d6) ꢀ: 163.5 (C-7), 156.4
(C-2), 146.8 (C-8), 134.5 (C-6), 132.7 (C-4), 130.8 (C-12), 128.6 (C-11), 128.3 (C-3),
127.5 (C-5), 127.1 (C-9), 122.7 (C-13), 118.3 (C-1), 38.2 (CH3O), 28.1 (CH2), 20.2
11
(CH3arom) ppm. B NMR (64 MHz, DMSO-d6) ꢀ: 1.0 ppm (h1/2 = 3852 Hz). Elemental
Anal. Calc. for C93H84B6N6O12: C 71.41, H 5.48, N 5.44 %. Found: C 71.37, H 5.41, N 5.27
%. 1542.57
Compound 13 was prepared from 0.020 g (0.13 mmol) of 3-aminophenylboronic acid
monohydrate and 0.020 g (0.066 mmol) of ligand 9 in ethanol. The product was obtained as
-1
v
a yellow powder. Yield: 0.006 g (16 %); m.p. > 360 °C. IR (KBr) (cm ): 3451 (s), 1622
(C=N, s), 1539 (w), 1389 (w), 1303 (w), 1183 (w), 1119 (w), 993 (w), 584 (w). FAB+-MS
m/z (%): 1681 ([M]+, 5), 1652 (5), 1636 ([M-OEt]+, 55), 1635 (38), 1606 (5), 1591 (5),
1562 (4), 460 (48), 307 (100), 289 (61), 219 (25). 1H NMR (200 MHz, DMSO-d6) ꢀ: 8.88

(6H, s, H-7), 8.19 (6H, s, H-9), 7.77 (6H, d, J = 8.0 Hz, H-11), 7.68 (6H, t, J = 8.0 Hz, H-
12), 7.56 (6H, d, J = 8.8 Hz, H-6), 7.42 (6H, d, J = 8.0 Hz, H-13), 6.61 (6H, dd, J = 8.8, 2.4
Hz, H-5), 6.56 (6H, d, J = 2.4 Hz, H-3), 4.40 (12H, s, CH2CH2O), 3.49-3.29 (12H, m,
13
CH3CH2O), 1.05 (18H, t, J = 7.0 Hz, CH3CH2O) ppm. C NMR (50 MHz, DMSO-d6) ꢀ:
163.9 (C-7), 163.2 (C-4), 162.7 (C-2), 147.5 (C-8), 134.8 (C-11), 133.0 (C-6), 129.2 (C-
12), 127.4 (C-9), 123.2 (C-13), 113.9 (C-1), 107.9 (C-5), 102.1 (C-3), 67.2 (CH2CH2O),
56.8 (CH3CH2O), 19.3 (CH3CH2O) ppm. 11B NMR (64 MHz, DMSO-d6) ꢀ: 1.0 ppm (h1/2 =
1920 Hz). Elemental Anal. Calc. for C96H90B6N6O18: C 68.60, H 5.39, N 5.00 %. Found: C
68.32, H 5.22, N 4.89 %.
Compound 14 was prepared from 0.027 g (0.18 mmol) of 3-aminophenylboronic acid
monohydrate and 0.029 g (0.09 mmol) of ligand 10 in ethanol. The product was obtained as
-1
v
a yellow powder. Yield: 0.014 g (27 %); m.p. > 360 °C. IR (KBr) (cm ): 3861 (w), 3439
(s), 2857 (w), 1618 (C=N, s), 1542 (w), 1382 (w), 1299 (w), 1112 (w), 988 (w), 905 (w),
835 (w), 787 (w), 558 (w). FAB+-MS m/z (%): 1723 (M+, 5) 1681 (4), 1677 ([M-OEt]+, 19),
1649 (4), 1632 (6), 1631 (5), 1604 (4), 704 (5), 524 (15), 443 (11), 307 (100), 266 (99), 240
(54). 1H NMR (400 MHz, DMSO-d6) ꢀ: 8.89 (6H, s, H-7), 8.18 (6H, s, H-9), 7.76 (6H, d, J
= 8.8 Hz, H-11), 7.68 (6H, t, J = 8.8 Hz, H-12), 7.55 (6H, d, J = 9.6 Hz, H-6), 7.40 (6H, d,
J = 8.8 Hz, H-13), 6.58 (6H, dd, J = 9.6, 2.4 Hz, H-5), 6.53 (6H, d, J = 2.4 Hz, H-3), 4.20
(12H, t, J = 5.2 Hz, CH2CH2O), 3.35-3.25 (12H, m, CH3CH2O), 1.23 (18H, s, CH3CH2O),
0.90-0.81 (6H, m, CH2CH2O) ppm. Elemental Anal. Calc. for C99H96B6N6O18: C 69.02, H
5.61, N 4.87 %. Found: C 68.97, H 5.52, N 4.80 %.
Compound 15 was prepared from 0.08 g (0.51 mmol) of 3-aminophenylboronic acid
monohydrate and 0.10 g (0.26 mmol) of ligand 11 in methanol. The product was obtained
-1
v
as a yellow powder. Yield: 0.109 g (68 %); m.p. > 360 °C. IR (KBr) (cm ): 3429 (s),
2369 (w), 1621 (C=N, s), 1542 (w), 1388 (m), 1180 (w), 1122 (w), 1002 (w), 797 (w), 704
(w), 475 (w). FAB+-MS m/z (%): 1794 ([M-OMe]+, 7), 1632 (15), 1542 (16), 1030 (28),
1
814 (15), 624 (17), 448 (12), 307 (100), 272 (38). H NMR (400 MHz, DMSO-d6) ꢀ: 8.87
(6H, s, H-7), 8.18 (6H, s, H-9), 7.76 (6H, d, J = 7.1 Hz, H-11), 7.70 (6H, t, J = 7.1 Hz, H-
12), 7.55 (6H, d, J = 8.5 Hz, H-6), 7.50 (12H, s, CHarom), 7.41 (6H, d, J = 7.1 Hz, H-13),
6.63 (6H, d, J = 8.5 Hz, H-5), 6.58 (6H, s, H-3), 5.19 (12H, s, CH2O), 3.37 (18H, s, CH3O)

ppm.13C NMR (100 MHz, DMSO-d6) ꢀ: 163.9 (C-7), 163.1 (C-4), 162.7 (C-2), 147.5 (C-
8), 137.0 (CCH2), 134.7 (C-11), 133.0 (C-6), 129.2 (C-12), 128.6 (CHarom), 127.5 (C-9),
11
123.1 (C-13), 113.8 (C-1), 108.1 (C-5), 102.5 (C-3), 69.9 (CH2O), 31.4 (CH3O) ppm. B
NMR (64 MHz, DMSO-d6) ꢀ: 2 ppm (h1/2 = 1920 Hz). Elemental Anal. Calc. for
C108H90B6N6O18: C 71.08, H 4.97, N 4.60 %. Found: C 70.97, H 5.01, N 4.57 %.
Acknowledgments
The authors thank Consejo Nacional de Ciencia y Tecnología (CONACyT) for financial
support. Project number: 157743.
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[27] X.-Y. Li, K.-Y. Yu, X.-L. Zhao, M.-L. Ma, F. Guo, X.-Q. Mi, B. Jiang, K. Wen Cryst.
Eng. Comm., 14 (2012) 7869-7871.
[28] J. Morales-Sanfrutos, M. Ortega-Muñoz, J. Lopez-Jaramillo, F. Hernandez-Mateo, F.
Santoyo-Gonzalez, J. Org. Chem., 73 (2008) 7768-7771.
[29] V. Barba, H. Höpfl, N. Farfán, R. Santillan, H.I. Beltran, L.S. Zamudio, Chem.
Commun., 24 (2004) 2834-2835.
[30] V. Barba, R. Villamil, R. Luna, C. Godoy-Alcántar, H. Höpfl, H. I. Beltran, L. S.
Zamudio-Rivera, R. Santillan, N. Farfán. Inorg. Chem., 45, 2006, 2553-2561.
[31] V. Barba, E. Gallegos, R. Santillan, N. Farfán, J. Organomet. Chem., 622 (2001) 259-
264.
[32] V. Barba, R. Hernández, H. Höpfl, R. Santillan, N. Farfán, J. Organomet. Chem., 694
(2009) 2127-2133.

[33] V. Barba, I. Betanzos. J. Organomet. Chem., 692 (2007) 4903-4908.
[34] N, Nishimura, K. Kobayashi, J. Org. Chem. 75 (2010) 6079-6085.
[35] N. Fujita, S. Shinkai, T. D. James, Chem. Asian J., 3 (2008) 1076-1091.
[36] R. Nishiyabu, Y. Kubo, T. D. James, J. S. Fossey, Chem. Commun., 47 (2011) 1124-
1150.
[37] K. Severin, Dalton Trans., (2009) 5254-5264.
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Chem., 65 (2009) 305-315.
[41] Crystal data for 10 (C17H16O6): CCDC number 916398, Orthorhombic, space group
P2(1)2(1)2, a = 6.787(3)), b =23.691(10), c = 4.5084(19) A˚ , a = b = c = 90.00°, V =
724.9(5) Å3, T = 100 K, Z = 2, 2341 reflections measured, 773 unique, (Rint = 0.04), R1
[I > 2ꢂI] = 0.04, wR2 = 0.08 for all data.
[42] Geometry optimization was done using HyperChem 8.0.7.
[43] Bruker Analytical X-ray Systems. SHELXTL-NT Version 6.10, 2000.

Schemes and Figures
Boroncalix[3]arenes
B(OH)2
O
3
3
OH
NH2
R
Double cone conformation
Boronhemicarcerands
X
O
O
3
X
X
OH
HO
+
B(OH)2
X
6
NH2
Double
calixarene
Linkers
Double
Calixarene
Scheme 1: Strategy to synthesized calix- (up) and hemicarcerand- (Down) like compounds
R
12
11
O
10
13
B
R'O
B(OH)2
N
7
6
3
8
9
O
5
R'OH/Benzene
N
1
+
3
3
OR'
∆
B
4 h
4
OH
2
NH2
O
R'O
N
R
R
B
O
R
R'
1: 5-Br
Me
Me
R
2
: 5-Me
3: 4-(Et2N) Me
4: 4-(Et2N) Et
Scheme 2: Synthesis of calix-like compounds

OH
HO
N
P
O
12
11
9
O
P
O
O
B
R'O
O
B
EtO
O
13
HO
6
10
N
HO
7
5
3
8
N
4
N
1
N
B
OR'
N
B
OEt
2
O
R'O
N
O
EtO
N
B
B
O
O
N
6: R = Me
7: R = Et
5
O
OH
OH
P
O
Scheme 3: Naphthalene and pyridoxal derivatives calix-like compounds
10
9MeO
11
CH3
B
O
OH
OH O
12
8
N
O
8
B(OH)2
2
MeOH/Benzene
13
1
2
5
7
1
7
3
4
+
6
3
4
3
∆
4 h
O
6
6
N
B
5
NH2
CH3
CH3
OMe
CH3
12
3
8
Scheme 4: Formation of hemicarcerand derived from bis-salicylaldehyde having CH2
groups as linkers

R
B(OH)2
5
6
7
3
+
6
O
O
1
4
O
O
2
3
NH2
HO
OH
9-11
R'OH/C6H6
∆ 4 h
R'
O
R
O B
9
2
6
3
10
O
N
N
B
11
O
1
8
13
4
7
12
O
5
O
3
R'
R
R'
13
14
15
: -CH2CH2-
Et
Et
: -CH2CH2CH2-
:
-CH C H CH - Me
p
2
6
4
2
Scheme 5: Synthesis of hemicarcerands having large chain linkers
Figure 1: Molecular structure for compound 10, ellipsoids are in a 50% of probability.
Selected bond distances (Å) and angles (°): C1-O1 1.356(4), C7-O2 1.239(4), C5-O3
1.362(4), C8-O3 1.449(4), C8-C9 1.508(4), C9-C8-O3 105.7(2), C8-O3-C5 118.6(3).

Figure 2: Side view of the unit cell for compound 10 showing a zig-zag ordering.
Figure 3: Part of the FAB+-MS Spectrum for compound 14 showing the molecular ion.
Inset, calculate isotopic pattern.

Figure 4: Molecular models for compounds 13, 14 and 15, illustrating the cavity distortion
arrangement.

!ꢀꢁꢂꢃꢄꢅꢂ
One-pot synthesis of calixarene and hemicarcerand like compounds can be modulated by
use of mono- or bis-salicylaldehyde derivatives respectively reacting withꢀꢁ
ꢂꢃ ꢄꢅꢆ ꢇꢈꢅꢉꢊꢋꢆꢌꢆꢅꢄꢍ ꢂꢍꢄꢎ. Both, calixarene and hemicarcerand compounds are result from
condensation reactions, wherein the formation of N-B coordination bonds plays a
significant role on the formation of macrocyclic products.

Graphical abstract
tꢄꢍꢏꢆꢐꢌꢂꢃ
wꢈꢑꢈꢂꢌꢍꢇ ꢇꢄꢐꢇꢊꢄꢐꢇꢏꢑ
ꢒ h ꢅꢈꢁ ꢆꢏ ꢑꢉꢅꢏꢇꢈꢑꢄꢑ ꢆꢓ ꢍꢂꢊꢄꢔꢂꢌꢈꢅꢈ ꢂꢅꢎ ꢇꢈꢃ ꢄꢍꢂꢌꢍꢈꢌꢂꢅꢎꢁꢊꢄꢕꢈ ꢍꢆꢃ ꢆꢖꢅꢎꢑꢗ ꢒ Iꢄꢐꢇ ꢍꢆꢅꢈ ꢍꢆꢅꢓꢆꢌꢃ ꢂꢏꢄꢆꢅ
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ꢑꢖꢋꢑꢏꢄꢏꢖꢈꢅꢏꢑꢗ ꢒ a ꢆꢎꢖꢊꢂꢏꢄꢆꢅ ꢆꢓ ꢏꢇꢈ ꢑꢄ!ꢈ ꢍꢂꢘꢄꢏꢉ ꢓꢆꢌ ꢇꢈꢃ ꢄꢍꢂꢌꢍꢈꢌꢂꢅꢎꢑ ꢋꢉ ꢍꢇꢂꢅꢐꢄꢅꢐ ꢏꢇꢈ ꢑꢄ!ꢈ ꢆꢓ ꢏꢇꢈ
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