5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene: Crystal structure and pH sensing properties

Article abstract of DOI:10.1002/cjoc.201090306

Treatment of 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene (2) with HCl in DMF or NaOH in MeOH produced 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]-arene·4DMF (2·4DMF) and 5,11,17,23-tetrak

Full text of DOI:10.1002/cjoc.201090306

FULL PAPER
5
,11,17,23-Tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetra-
hydroxy Calix[4]arene: Crystal Structure and
pH Sensing Properties
a
a
a
Liu, Leilei (刘雷雷)
Ren, Zhigang (任志刚)
Li, Hongxi (李红喜)
a
,a,b
Shang, Hai (尚海)
Lang, Jianping* (郎建平)
a
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and
Materials Science, Suzhou University, Suzhou, Jiangsu 215123, China
b
State Key Laboratory of Oraganometallic Chemistry, Shanghai Institute of Organic Chemisty, Chinese Academy
of Sciences, Shanghai 200032, China
Treatment of 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene (2) with HCl in
DMF or NaOH in MeOH produced 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxycalix[4]-
arene•4DMF (2•4DMF) and 5,11,17,23-tetrakis[(p-carboxyphenylsodium)azo]-25,26,27,28-tetrahydroxycalix[4]-
1
13
arene (3), respectively, which were characterized by elemental analysis, IR, UV-vis, H NMR and C NMR. An
X-ray analysis of 2•4DMF revealed that its calix[4]arene core adopts a flattened cone conformation in which op-
posed phenyl groups take parallel or sharply inclined positions. The intra- and intermolecular hydrogen-bonding in-
teractions and the π…π interactions form a 2D hydrogen-bonded wavelike network. Compound 2 had a unique re-
versible color change in a wide pH range from 1 to 13.5 and showed interesting pH sensing properties.
Keywords p-carboxyphenylazocalix[4]arene, synthesis, crystal structure, NMR shift, pH sensing properties
Introduction
On the other hand, a number of azocalix[4]arene de-
1
9-25
rivatives have recently been prepared,
and employed
1
-3
The design and construction of chemical sensors
19-24
for the recognition of metal ions
and the discrimina-
for the visual discrimination of varied pH values has
aroused much attention due to their increasing applica-
tions in the common chemical reactions, environmental
technology and biological technology. As a good
chemosensor, it should exhibit an appropriate, rapid and
25
tion of different types of amines, but scarcely explored
for their pH sensing properties. Compound 25,26,27,28-
26
tetrahydroxycalix[4]arene (1) was employed to pre-
4
-7
pare an azocalix[4]arene derivative with four carboxyl
groups, 5,11,17,23-tetrakis[(p-carboxyphenyl)azo]-25,
＋
reversible response towards H in a wide pH range and
27
2
6,27,28-tetrahydroxycalix[4]arene (2). However, its
should not affect the ongoing measurement. So far, a
number of pH sensing compounds have been synthe-
crystal structure has not been determined yet and its pH
sensing properties are virtually unknown. We are inter-
ested in the physical and chemical properties of azo-
calix[4]arene derivatives with proton donor-acceptor
groups. We found that 2 could respond to different pH
values ranged from 1 to 13.5. This conversion between
8
-18
sized,
some of which showed potential application as
the pH probes. These pH sensing compounds were usu-
ally functioned via one or two pairs of proton do-
nor-acceptor groups such as R
＋
13,14
－
2
R
1 2
R
3
NH … CO .
Those with two pairs of proton donor-acceptor groups
2
and its sodium salt 3 (Scheme 1) was reversible ac-
＋
15-18
－
2
like CO … R
1
R
2
R
3
NH … N… OH
seemed more
companying an intriguing reversible color change. In
this paper, we report the crystal structure of 2•4DMF
and its pH sensing properties.
sensitive than those with one pair of proton donor-ac-
ceptor groups. However, most of the aforementioned pH
sensing compounds showed a relatively narrow pH re-
gion from 5 to 9. In fact, few examples were involved in
the lower pH region (pH＜ 5) or the higher pH region
Experimental
(
pH＞ 9). Moreover, compounds with three or four pairs
Materials and physical measurements
of proton donor-acceptor groups were less explored for
their pH sensing properties.
Compounds 1 and 2 were prepared according to the
*
E-mail: jplang@suda.edu.cn; Tel.: 0086-0512-65882865; Fax: 0086-0512-65880089
Received January 9, 2010; revised March 28, 2010; accepted May 20, 2010.
Project supported by the National Natural Science Foundation of China (Nos. 20525101 and 20871088), the State Key Laboratory of Organometallic
Chemistry of Shanghai Institute of Organic Chemistry (Grant 08-25), the Qin-Lan Project of Jiangsu Province, and the SooChow Scholar Program
and Program for Innovative Research Team of Suzhou University.
Chin. J. Chem. 2010, 28, 1829— 1834
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1829

Liu et al.
FULL PAPER
Scheme 1 Synthesis of 2 from 1 and pH-directed conversion between 2 and 3
2
6,27
3
－1
literature methods.
Other chemicals and reagents
flow rate of 100 cm •min (N
2
). All potentiometric
were obtained from commercial sources and used as
received. DMF was freshly distilled under reduced
pressure, while the water that was used for potentiomet-
ric titration was deionized water. IR spectra were re-
corded with a Varian 1000 FT-IR spectrometer as KBr
titrations were run at 20 ℃ with stirring, and the con-
－
1
centrations of NaOH (0.0103 and 0.1008 mol•L ) were
2
8
2 2
calibrated respectively by (COOH) •2H O. To cali-
brate the pH meter [Mettler-Toledo LAB pH (FE20)] at
the elevated temperature, a three-point calibration was
made prior to each experiment using METTLER
TOLEDO standard buffer solutions (pH 4.01 at 25 ℃;
pH 7.00 at 25 ℃; pH 10.01 at 25 ℃), which had a
known pH at each temperature studied.
－
1
disks (4000—400 cm ). The elemental analyses for C,
H and N were performed on an EA1110 CHNS elemen-
tal analyzer. UV-Vis spectra were measured with a
1
13
Varian 50 UV/Vis spectrophotometer. H and C NMR
spectra were recorded at ambient temperature with a
1
Preparation of 5,11,17,23-tetrakis[(p-carboxyphen-
Varian UNITYplus-400 spectrometer. The H NMR
yl)azo]-25,26,27,28-tetrahydroxycalix[4]arene•4DMF
chemical shifts were reported relative to TMS in
(
2•4DMF)
1
3
(
CD
3
)
2
SO. The C NMR chemical shifts were refer-
SO signal. The thermal analysis was
To a yellow solution of 2 (51 mg, 0.05 mmol) in
enced to the (CD )
3 2
－
1
DMF (5 mL) was added five drops HCl (1 mol•L ).
The solution turned to red immediately. After being
stirred at room temperature for 2 h, the resulting solu-
carried out with a Perkin-Elmer TGA-7 thermogravim-
etric analyzer at a heating rate of 5 ℃•min－ and a
1
1
830
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1829— 1834

5
,11,17,23-Tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene
tion was filtered. Diethyl ether (30 mL) was carefully
layered onto the filtrate to form red blocks of 2•4DMF
tions were measured in the range of 3.31º＜θ＜25.00º,
of which 5643 were unique (Rint＝0.0729). The col-
lected data were reduced by using the program Crystal-
Clear (Rigaku and MSC, Ver.1.3, 2001), and an em-
pirical absorption correction (multi-scan) was applied,
resulting in the transmission factors ranging from 0.968
to 0.983. The reflection data was also corrected for
Lorentz and polarization effects.
for one week, which were collected by filtration and
1
dried in air. Yield 45 mg (68.7%); H NMR (DMSO-d
6
,
4
00 MHz) δ: 8.04 (d, J＝8 Hz, 8H, ArH-a), 7.95 (s, 4H,
CHO), 7.84 (s, 8H, ArH-c), 7.81 (d, J＝8 Hz, 8H,
ArH-b), 3.66—4.71 (8H, CH
2 3
), 2.88 (s, 12H, NCH ),
1
3
2
1
1
2
3 6
.73 (s, 12H, NCH ); C NMR (DMSO-d , 400 MHz) δ:
66.75, 162.27, 154.68, 144.71, 131.28, 130.51, 130.41,
24.20, 121.88, 35.76, 30.75; IR (KBr) ν: 3419 (m),
930 (w), 1715 (s), 1680 (s), 1668 (s), 1602 (s), 1525
The crystal structure of 2•4DMF was solved by di-
2
9
rect method applying SHELXTL-97 program and re-
2
fined by full matrix least-square on F . For 2•4DMF,
(
m), 1469 (m), 1415 (m), 1386 (m), 1331 (m), 1265 (vs),
one azobenzene group and one DMF solvent molecule
were found to be disordered over two positions with an
occupancy factor of 0.523/0.477 for N3/N3A, N4/N4A,
C22-C27/C22A-C27A, O8/O8A, N6/N6A, and C32-
C34/C32A-C34A. All non-hydrogen atoms were refined
1
5
5
165 (w), 1116 (m), 864 (w), 777 (w), 697 (w), 667 (w),
－
1
35 (w) cm . Anal. calcd for C68
H
68
O
16
N
12: C 62.38, H
.23, N 12.84; found C 62.57, H 5.17, N 12.53.
Preparation of 5,11,17,23-tetrakis[(p-carboxyphenyl-
2
anisotropically. The H atoms of the CO H groups and
sodium)azo]-25,26,27,28-tetrahydroxycalix[4]arene
one of the hydroxyl groups were located from Fourier
maps. All other H atoms were placed in the geometri-
cally idealized positions [d(O — H) ＝ 0.83 Å, with
(
3)
To a yellow solution of 2 (51 mg, 0.05 mmol) in
MeOH (3 mL) was added solution of NaOH (0.2 mL, 1
mol•L , 0.2 mmol). The solution turned to deep red
immediately, and was briefly stirred and filtered. EtOH
U
iso(H)＝1.5Ueq(C) for hydroxyl groups; d(C—H)＝
－
1
0
.97 Å, with Uiso(H)＝1.5Ueq(C) for methyl groups; d(C
—
H)＝0.98 Å, with Uiso(H)＝1.2Ueq(C) for methylene
(
20 mL) was carefully layered onto the filtrate to form
deep red crystals of 3 for 3 d, which were collected by
filtration, washed with EtOH and Et O and dried in air.
Yield 40 mg (72.4%); H NMR (DMSO-d , 400 MHz) δ:
groups; d(C—H)＝0.94 Å, with Uiso(H)＝1.2Ueq(C) for
methine groups; d(C—H)＝0.94 Å, with Uiso(H)＝1.2
2
eq(C) for phenyl groups] and constrained to ride on
U
1
6
their parent atoms. The final refinement based on 4098
observed reflections with I＞2σ(I) and 518 variable pa-
rameters converged to R＝0.1260, wR＝0.2916 (w＝
7
(
.93 (d, J＝8 Hz, 8H, ArH-a), 7.72 (s, 8H, ArH-c), 7.64
1
3
d, J＝8 Hz, 8H, ArH-b), 3.63—4.42 (m, 8H, CH
2
); C
2
2
2
2
2 6
NMR [D O (0.1 mL) and DMSO-d (0.5 mL), 400 MHz]
δ: 164.61, 159.73, 154.14, 145.59, 140.49, 132.00,
1
2
1/[σ (F
o
)＋(0.0878P) ＋15.5855P], where P＝(F
o
2
c
＋
2F
)/3), S＝1.196, (∆/σ)max＝0.005, (∆ρ)max＝0.517
3
31.11, 124.71, 122.41, 32.93; IR (KBr) ν: 3417 (m),
932 (w), 1653 (m), 1595 (vs), 1549 (s), 1473 (w), 1386
and (∆ρ)min＝－0.241 e/Å .
The crystallographic data have been deposited with
the Cambridge Crystallographic Data Centre as supple-
mentary publication number CCDC No. 736244. Cpoies
of the data can be obtained, free of charge, on applica-
tion to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (Fax: ＋44 1223 336033; E-mail: deposit@ccdc.
cam.ac.uk or http://www.ccdc.cam.ac.uk).
(vs), 1295 (m), 1272 (m), 1136 (w), 1117 (m), 870 (w),
－
1
8
42 (w), 794 (m), 703 (w), 635 (w) cm . Anal. calcd
for C56
6
H
36
O
12
N
8
4
Na : C 60.87, H 3.28, N 10.14; found C
0.57, H 3.18, N 10.63.
X-ray structure determination
All measurements were made on a Rigaku Mercury
CCD X-ray diffractometer by using graphite mono-
chromated Mo Kα (λ＝0.71073 Å). Single crystals of
Results and discussion
2
•4DMF suitable for X-ray analysis were obtained di-
Treatment of 2 with HCl in DMF followed by dif-
fusing diethyl ether into the solution produced 2•4DMF
as red blocks, while its reactions with NaOH in MeOH
afforded a tetrasodium salt 3 as deep red crystals.
Compounds 2•4DMF and 3 were relatively stable to-
ward oxygen and moisture, and soluble in DMF and
DMSO. The elemental analysis of 2•4DMF and 3 were
consistent with their chemical formula.
rectly from the above preparation. A red blocks of
2
•4DMF with dimensions 0.44 mm×0.28 mm×0.20
mm was mounted at the top of a glass fiber with grease,
and cooled at 223 K in a liquid-nitrogen stream. Dif-
fraction data were collected at ω mode with a detector
distance of 35 mm to the crystal. Indexing was per-
formed from 6 images, each of which was exposed for 5
s. Cell parameter was refined by using the program
CrystalClear (Rigakuand MSC, version 1.3, 2001) on
all observed reflections between θ of 3.056° and 25.0°.
IR and NMR spectra
In the IR spectra of 2•4DMF and 3 (Figure S1 and
S2), there exists a very strong and broad O—H stretch-
68 12 16
Its crystal data are described as follows: C68H N O ,
－
1
FW ＝ 1309.4, monoclinic, space group C2/c, a ＝
ing vibration at 3417—3419 cm . Similar band was
30
2
1
1
4.034(5) Å, b＝8.8591(18) Å, c＝30.989(6) Å, β＝
also found in calix[4]arene-p-tetrasulphnonic acid,
3
03.22(3)°, V＝6423(2) Å , Z＝4, F(000)＝2752, D
c
＝
implying that the OH groups in 3 kept intact. The N＝N
－
3
－1
－1
.354 g•cm , µ＝0.098 mm . A total of 20378 reflec-
and C＝O stretching vibrations at 1680/1668 cm (2•
Chin. J. Chem. 2010, 28, 1829— 1834
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1831

Liu et al.
FULL PAPER
3
2
4
DMF) were shifted relative to those of 3 (1653/1595
tetrahydroxy calix[4]arene. The mean C—O [1.307(7)
Å] and C＝O [1.209(6) Å] bond lengths of carboxyl
groups of 2•4DMF (Table S1) were normal relative to
－
1
cm ), which may be due to the deprotonation of
1
2
•4DMF. The H NMR spectrum of 2•4DMF in
3
3,34
DMSO-d measured at ambient temperature showed the
6
those found in calix[4]arenecarboxylic acids.
Each
correct aromatic/DMF proton ratios for 2 and four DMF
solvent molecules. The H NMR spectrum of 3 in
DMSO-d exhibited a singlet and two doublets for the
6
azo group adopts a trans-configuration. The mean N＝
N [1.296(4) Å] bond length of 2•4DMF is 0.03—0.08 Å
elongated relative to those observed in 26,28-bis[((di-
ethylamino)carbonyl)methoxy]-25,27-dioxy-5,11,17,23-
tetrakis(phenylazo)calix[4]arene-(ethylacetate-O)-potass-
1
phenyl group at δ 7.72 (ArH-c), δ 7.92—7.94 (ArH-a),
δ 7.63—7.65 (ArH-b), and the methylene groups at
δ 3.63—4.42. Interestingly, slow addition of 4 equiv. of
2
4
ium (1.267(2) Å) and 5,11,17,23-tetrakis(phenylazo)-
－
1
32
NaOH to a solution of 2 (0.1 mol•L ) in DMSO-d
6
/
25,26,27,28 -tetrahydroxycalix[4]arene (1.244(2) Å).
2
D O made its solution color be turned from yellow to
light red, red, and deep red (3), which were monitored
1
by H NMR spectra at ambient temperature (Figure 1).
It showed that the signals of proton a (δ 8.04—8.06), b
(
δ 7.81—7.83), and c (δ 7.84) had a distinct upfield shift
relative to those of proton a' (δ 7.92—7.94), b' (δ 7.63—
7
.65), and c' (δ 7.72) of 3 upon addition of NaOH. Such
shifts might be ascribed to the more conjugation be-
－
2
tween the more naked CO groups and the azoben-
3
1
zenecalix[4]arene core. In addition, the sharp signals
of 2 gradually turned into the broad ones of 3, suggest-
ing that there existed a proton exchange equilibrium
between the two compounds.
Figure 2 View of the molecular structure of 2 with labeling
scheme and 30% thermal ellipsoids. Only one of the disordered
azobenzene group is shown. Symmetry code: A, －x ＋1, y, －z
＋
3/2.
In the crystal of 2•4DMF, two intramolecular
H-bonding interactions between the two hydroxyl
groups in 25,26,27,28-tetrahydroxycalix[4]arene
[
O(1)…O(2)] and between one phenyl group and the O
atom of the DMF solvent molecule [C(5)…O(8)] are
observed. In addition, three intermolecular H-bonding
interactions between the O atom of the carboxylate
group and the O atom of the DMF molecule [O(3)…O(7)
(
x, y, 1＋z)] and between the methyl group and the O
1
atom of the carboxylate group [C(30)…O(6) (1－x, 2－
y, 1－z)] and between the O atoms of the carboxylate
groups [O(5)…O(4) (1－x, 2－y, 1－z)] produce a 1D
H-bonded double chain (Figure 3a). Furthermore, each
chain is linked via evident π…π interactions (3.459
Figure 1 The H NMR signals of proton a, b, and c of 2 show-
ing upfield shifts relative to those of proton a', b', and c' of 3 upon
－
1
addition of NaOH. Line 1: 2 (0.1 mol•L ); Line 2: 2＋NaOH;
Line 3: 2＋2NaOH; Line 4: 2＋3NaOH; Line 5: 2＋4NaOH＝3.
33,34
Å)
between each phenyl group of azobenzene moie-
Crystal structure
ties, thereby forming a 2D H-bonded wave-like network
The identities of 2•4DMF was further confirmed by
X-ray crystallography, but attempts to grow better sin-
gle crystals of 3 always failed. 2•4DMF crystallizes in
the monoclinic space group C2/c, and its asymmetric
unit consists of half of 5,11,17,23-tetrakis[(p-carboxy-
phenyl)azo]-25,26,27,28-tetrahydroxycalix[4]arene and
two DMF solvent molecules. The calix[4]arene core of
(
Figure 3b).
Thermogravimetric analysis (TGA)
The thermal analysis of 2•4DMF was carried out
with a Perkin-Elmer TGA-7 thermogravimetric analyzer
－1
at a heating rate of 5 ℃•min and a flow rate of 100
3
－1
cm •min (N
2
). Its TGA curve showed two stages of
2
adopts a flattened cone conformation in which op-
release of DMF solvent molecules (Figure S3). The first
weight loss of 10.70% at 35.90 ℃ corresponds to the
loss of two DMF solvent molecules (calculated 11.16%).
The second weight loss (11.60%) in the range of 35.90
posed phenyl rings have parallel or sharply inclined po-
sitions (Figure 2), which were observed in some calix-
[4]arene derivatives such as 5,17-bis(p-methoxyphenyl-
azo)-26,28-dihydroxy-25,27-bis(propargyloxy) calix[4]-
—
149.90 ℃ approximately amounts to the loss of the
2
2
arene and 5,11,17,23-tetrakis(phenylazo)-25,26,27,28-
1
832
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1829— 1834

5
,11,17,23-Tetrakis[(p-carboxyphenyl)azo]-25,26,27,28-tetrahydroxy calix[4]arene
other two DMF solvents (calculated 11.16%). The re-
sults also confirmed that 2 was solvated by four DMF
solvent molecules.
Figure 3 (a) View of one section of the 1D H-bonded double
chain (looking along the c-axis) formed by intra- and in-
ter-molecular H-bonding interactions in 2•4DMF. (b) View of the
2D H-bonded wave-like network (extending along the ac plane)
formed by intra- and inter-molecular H-bonding and π…π inter-
－
5
－
1
actions.
Figure 4 (a) UV-vis spectra of 2 (4×10 •mol•L ) titrated
with a dilute NaOH solution. (b) Color changes corresponding to
UV-vis spectra
different pH values [0.1 mL of 2 (1.7 g/L) in H O (10 mL)].
2
－
4
－1
The UV-vis spectra of 2 (1×10 mol•L ) titrated
－
2
－1
of 2•4DMF and 3 from treatment of 2 with HCl or
NaOH. 2•4DMF contains a 2D H-bonded wavelike net-
work formed by the intra- and intermolecular
with diluted NaOH solution (5×10 mol•L ) was
measured at room temperature (Figure 4a). Compound 2
was characterized by three absorptions. One peak at 265
nm and one broad peak at 360 nm may be assignable to
the transition between the phenyl moiety and the π-π*
H-bonding interactions along with the π…π interactions.
＋
Compound 2 responded to H in a wide pH range from
3
5
1
to 13.5. The reversible conversion between 2 and 3
transition of trans-azobenzene groups, while the weak
peak at 526 nm may be due to the n-π* transition of the
went along with a unique reversible color change. The
results suggested that 2 may have a potential application
as a good pH sensor. Studies on the respect of research
are underway in our laboratory.
＋
36
—
N＝N —H moieties. Upon addition of base, the
two absorption maxima at 265 and 360 nm gradually
increased in intensity and the absorption at 526 nm
gradually disappeared accompanying appearance of one
shoulder absorption at 442 nm. These changes may be
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7
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8
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4
－ 39
H L to L . During the titration of 2 with diluted
4
NaOH solution, the corresponding color changes with
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Figure 4b. When the solution of 3 was titrated with HCl
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Conclusion
2
In conclusion, we have demonstrated the preparation
Chin. J. Chem. 2010, 28, 1829— 1834
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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