Sensors and Actuators B 177 (2013) 913923

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Functionalized azobenzocrown ethers as sensor materialsThe synthesis and ion
binding properties
Ewa Wagner-Wysiecka
a,
, Tomasz Rzymowski
a
, Mirosaw Szarmach
a
, Marina. S. Fonari
b
,
El zbieta Luboch
a,
a
Department of Chemical Technology, Faculty of Chemistry, Gdansk University of Technology, Narutowicza Street 11/12, 80-233 Gda nsk, Poland
b
Institute of Applied Physics, Academy of Sciences, Chis in au MD 2028, Republic of Moldova
a r t i c l e i n f o
Article history:
Received 5 June 2012
Received in revised form
17 November 2012
Accepted 19 November 2012
Available online 5 December 2012
Keywords:
Azobenzocrown ethers
Chromoionophores
Molecular recognition
Spectroscopic methods
Ion-selective electrodes
Screen printed electrodes
X-ray structure
a b s t r a c t
New 13- and 16-membered azobenzocrown ethers with aromatic amino, amide, etherester or
etheramide residue in para position to an azo moiety were obtained. Acidbase properties and ion
binding ability of the colored compounds were studied by spectroscopic methods: UVvis, uorimetry
and
1
H NMR spectroscopy. Selected azobenzocrowns were tested as ionophores in ion-selective mem-
brane electrodes (ISEs) classic and miniature all solid state. The X-ray structure of the sodium complex
of etherester derivative of 16-membered azobenzocrown was presented.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Supramolecular chemistry, taking its early inspiration from
Nature, is nowadays one of the most active eld of science [1,2]. It
covers, among others, the design, synthesis andstudies of the inter-
actions between host and guest molecules for chemical sensing
purposes. At the beginning, metal cation coordination chemistry
has been the main stream in supramolecular science. Since that
time, properties of many compounds of various structures have
been studied pointing the wide eld of their possible applica-
tions. Well known metal cation complexing agents are molecular
receptors based on crown ethers [3]. Among them an impor-
tant class is macrocyclic compounds containing an azo residue
[4]. Crown ethers incorporating azobenzene moiety as a part of
the macrocycle azobenzocrown ethers are interesting metal
ion complexing compounds. In addition, these macrocycles are
photo and redox active [57]. Numerous macrocyclic compounds
with inherent 2,2

-azobenzene [815] or 4,4

-azobenzene [16,17]
have been synthesized and exhaustively studied. Wide possibili-
ties of azobenzocrowns functionalization result in their potential

Corresponding authors. Tel.: +48 58 3471759; fax: +48 58 3411949.

E-mail addresses: ewa.wagner-wysiecka@pg.gda.pl (E. Wagner-Wysiecka),
elzluboc@pg.gda.pl, elub@chem.pg.gda.pl (E. Luboch).
applications in the variety of elds, e.g. lipophilic crowns may
be successfully used as ionophores, both in classic [11,12,18] and
miniature all solid state ion-selective membrane electrodes (ISEs)
[19]. As an azo group is an integral part of the macroring it can act
as a donor place in ion binding. This was conrmed, in a solid state,
by several reported X-ray structures of azobenzocrown complexes
with metal cations [1923]. Azoarylcrown ethers behave also as
chromoionophores selectively binding metal cations in solution
[2426]. Cationligand interactions are well manifested by color
and UVvis spectral changes. Further structure modication of the
azobenzocrown ethers skeleton can leads to compounds compris-
ing the merits of chromoionophores and uoroionophores [27]. It
is worth noting that some compounds mentioned above can be
concurrently used as good ionophores in membrane ion-selective
electrodes. It makes theman universal, to some extend, analytical
tool for eventual metal cation detection and/or determination.
Anion coordination is another important eld of interest in
supramolecular chemistry. This is, among others, because of anions
abundance in nature and their key role in many biochemical pro-
cesses. The design and synthesis of anion receptors are widely
presented in exhaustive reviewarticles [2834]. Depending on the
structure of receptor, the respective ligands may be used for partic-
ular chemical sensors construction or/and as selective reagents for
spectroscopic purposes [31,34]. It was foundthat ion-selectiveelec-
trodes with complexes of azothiacrown with heavy metal cations
0925-4005/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.snb.2012.11.068
914 E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923
(silver, mercury and copper) as ionophores showanionic response
[35]. Numerous examples of both neutral crowns and their metal
cation complexes of different structure have been reported up to
nowas anion receptors, for examples see [3640].
Here we present new functionalized azobenzocrown ethers of
different size of the macrocycle and their properties. The synthe-
sized 13- and 16-membered crowns have aromatic amino (1, 2) or
aromatic amide(3, 4), etherester (510), andetheramide(1316)
groups as a side residue located in para position to an azo moiety
(Scheme 1).
For selected macrocycles acidbase properties and complex-
ation studies were carried out by UVvis spectrophotometry,
uorimetry and
1
H NMR spectroscopy in acetonitrile. Ion bind-
ing properties were compared with data available for reference
compounds AH (Fig. 1) [9,10,18,24].
Additionally, N H group inuence on the possible anion bind-
ing was also investigated. Some more lipophilic compounds were
tested as ionophores in ion-selective membrane electrodes (ISEs)
classic and all solid state.
2. Experimental
2.1. General
All chemicals of highest available purity were purchased from
commercial sources and used without further purication. THF for
synthesis and membrane preparation was freshly distilled over
LiAlH
4
. TLC: aluminum sheets covered with silica gel 60F
254
were
purchased from Merck. For column chromatography silica gel 60
(0.0630.200mm) (Merck) was used.
1
Hand
13
CNMR spectra were
recorded at a Varian instrument (500 and 125MHz, respectively).
Chemical shifts are reported as [ppm] values in relation to TMS.
FTIR spectra were recorded on a Mattson Genesis II instrument.
Mass spectra were recorded onanAMD-604 (EI method, 70eV) and
aGCTPremier (TOFMSFD
+
) instruments. For UVvis measurements
an UNICAMUV300 apparatus was used. Fluorescence spectra were
recorded on an AMINCO-Bowman Series 2 luminescence spec-
trometer (ash xenon lamp). Bandpass at excitation and emission
monochromators: 16nm. Fluorescence spectra are uncorrected to
instrument response. Spectroscopic measurements were carried
out in acetonitrile (LiChrosolv

) of gradient grade. Deionized water

(18M!cm, Hydrolab, Poland) for water containing solvent system
for UVvis spectrophotometry and EMF measurements was used.
EMF measurements were carried out using a 16-channel Lawson
Lab potentiometer (USA). The screen-printed graphite electrodes
were preparedinInstitute of Electronic Materials Technology, War-
saw, Poland (plates of 1815mmwithsix electrodes, openings area
ca. 1mm
2
). All measurements were carried out at room tempera-
ture.
2.2. Syntheses
For synthetic details and spectral data, see Supplementary data
ST2.
2.3. Complexation studies
Complexationstudies were performedby UVvis titrationof the
ligand solution in acetonitrile with the respective metal perchlo-
rates (for metal cations) or tetra-n-butylammonium(TBA) salts (for
anions). Caution! Perchlorate salts should be regarded as potentially
explosive and handled with care. The stock solutions of azoben-
zocrowns (10
4
M) andmetal perchlorates or TBAsalts (10
2
M)
were prepared by weighing the respective quantities of them and
dissolving in acetonitrile in volumetric asks. Titrations were car-
ried out in a quartz cuvette with path length of 1cm keeping
constant volume of the ligand solution (2.3mL). The stability con-
stant values were calculated with the use of OPIUM [41] program
on the basis of titration experiment data.
2.4. Ion selective electrodes
2.4.1. Classic ISEs
The membrane components (8mg of ionophore, 50mg of PVC,
0.1mL of o-nitrophenyl-octyl ether (o-NPOE) and 1mg of potas-
sium tetrakis(4-chlorophenyl)borate (KTpClPB)) were dissolved in
freshly distilled, dry THF (1.2mL). The solution was poured into a
glass ring (diameter 15mm). After 1 day, membranes of d=7mm
were cut out and incorporated into Ag/AgCl electrode bodies of IS
type (Moeller S.A., Zurich, Switzerland). NaCl or KCl 10
2
M were
used as internal electrolyte for sodium and potassium selective
electrodes, respectively. The electrode was conditioned by soaking
it in a 10
2
Msolution of MCl (M the main ion) for 24h. A double-
junction Ag/AgCl, KCl 1M reference electrode (Monokrystaly RAE
112) was used with 1M NH
4
NO
3
solution in the bridge cell. The
selectivity coefcients (K
Na,K
, K
Na,H
or K
K,Na
, K
K,H
) were determined
using the separate solution method (SSM) [42] at ion activi-
ties of 10
1
M in neutral and 3% TRIS (pH9) for 13-membered
ionophores and neutral pH for electrodes with 16-membered ion-
carriers.
2.4.2. Screen-printed electrodes
Ionophore and ca. 0.05mg of carbon nanotubes (single wal-
let, Aldrich) in 1mL of THF were sonicated for 1h. Next, the
remaining membrane constituents were added as described above.
The solution (10.5L) was applied onto graphite screen-printed
electrodes and was left to dry over 24h at roomtemperature. Next
electrodes were conditioned by soaking themin a 10
3
Msolution
of NaCl or KCl for 10h. All the other experimental details were iden-
tical as described for classic electrodes. The measurements were
carried out in accordance with procedures specied for microfab-
ricated ion-selective electrodes [43].
The response of both classic and screen-printed electrodes
toward alkali (Li
+
, Na
+
, K
+
, Rb
+
, and Cs
+
), alkaline earth (Mg
2+
and
Ca
2+
) and ammonium(used as chlorides) ions was studied.
2.5. X-ray crystal structure determination
2.5.1. Preparation of crystals
Ethoxycarbonylbutylenoxy-16-azobenzocrown compound 8
(16.5mg, 0.055mmol) and sodium iodide (22mg, 0.055mmol)
were dissolved in methanol (5mL) and ltered. Filtrate was
evaporated under reduced pressure. To the obtained solid
acetone:propan-2-ol (1:1, v/v) mixture (2mL) was added. Very
slow solvent evaporation has resulted in crystals melting at
160166

C.
2.5.2. Determination of crystal structure
The X-ray data for [Na(8trans)]I complex were collected at
150KonaKM4CCDdiffractometer usinggraphite-monochromated
MoK radiation and were corrected for Lorentz and polarization
effects. The structure was solved by direct methods and rened
by full-matrix least squares technique based on F
2
. Analytical
numeric absorption correction using a multifaceted crystal model
based on expressions derived by Clark and Reid [44] was applied.
Non-hydrogen atoms were rened with anisotropic displacement
parameters. C-bound hydrogen atoms were placed in geometri-
cally calculated positions and rened using temperature factors
1.2 times those of their bonded carbon atoms. Calculations were
performed using SHELX-97 crystallographic software package.
E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923 915
OH
NH
2
O
O
O
N
N
NH
2
O H
OH
N
N
NH
2
O
O O
n
Ts Ts
O
O
O
N
N
NH
2
O
O
O
N
N
NH C
C
11
H
23
O
NH
2
O H
O
O
O
N
N
OH
O
O
O
N
N
O(CH
2
) C
O
OEt
O
O
O
N
N
O(CH
2
)
3
C
O
OH
O
O
O
N
N
O(CH
2
)
3
C
O
NHC
7
H
15
N H
2
OH
N
N
OH
O
O
O
N
N
OCH
2
C
O
NHC
7
H
15
ClCH
2
C
O
NHC
7
H
15
NaNO
2
HCl
n
tBuOK, THF
n
C
11
H
23
COCl, Et
3
N
THF
n
1. n = 1
2. n = 2
H
2
O, NaOH
3. n = 1
4. n = 2
C. n = 1
D. n = 2
n
Br(CH
2
)
m
COOEt
K
2
CO
3
, acetone
m
n
n
KOH
EtOH
C
7
H
15
NH
2
DMF, NEt
3
n
a)
b)
c)
17
5. n = 1, m = 1
6. n = 2, m = 1
7. n = 1, m = 3
8. n = 2, m = 3
9. n = 1, m = 5
10. n = 2, m = 5
11. n = 1
12. n = 2
15. n = 1
16. n = 2
+
18
DCC, HONSu
13. n = 1
14. n = 2
n
K
2
CO
3
, DMF
Scheme 1. The synthetic routes for compounds 116.
3. Results and discussion
3.1. Synthesis
Target compounds 110 and 1316 were prepared as shown
in Scheme 1ac. For synthetic details see Supplementary data, ST1
and ST2.
3.2. The properties of aromatic amino- and
amide-azobenzocrowns (tautomerism, solvatochromism,
acidbase properties)
In aromatic azo compounds substituted in ortho or para posi-
tion with hydroxyl or amino group intramolecular proton transfer
may occur. This phenomena was also observed for hydroxyazoben-
zocrowns studied earlier [18,24,47]. As amino group in 1 and 2
is located in para position to azo moiety, tautomeric equilibrium
canbe takenintoconsideration. Moreover, possible tautomerismof
N-acetyl derivatives of aminoazobenzocompounds was also taken
into account [48].
Solvent inuence on tautomeric equilibrium of aminoazoben-
zocrowns was studied by
1
H NMR spectroscopy. It was found
that in aprotic solvents such as acetonitrile (Fig. 2a) and DMSO
(Fig. 2b) 1 exists in aminoazoform. In
1
H NMR spectrum of
1 recorded in methanol and acetonitrile:water mixture (not
shown) aromatic proton signals distribution is similar to this
which was observed in DMSO. It also points that in these sol-
vents aminoazoform of 1 is dominating. Above observations can
lead to conclusion that tautomeric equilibrium of 1 is neutral
solvent independent. Similar experiments for 2 conrmed that
in acetonitrile, acetone and DMSO aminoazo form is dominat-
ing.
This is opposite to the properties of hydroxyazoben-
zocrowns studied ealier. A quinone-hydrazone equilibrium of
Fig. 1. The reference azobenzocrown ethers.
916 E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923
Fig. 2. The comparison of the
1
H NMR spectra (7.93.6ppm) of 1 recorded in: d-acetonitrile (a) and d-DMSO (b).
O
O
O
N
H
O
N
O
O
O
N
N
OH
O
O
O
N
H
NH
N
O
O
O
N
N
NH
2
C 1
Fig. 3. Tautomerismof hydroxy- (C) and aminoazobenzocrown (1) ethers exemplied with 13-membered azobenzocrowns.
hydroxyazobenzocrowns was found to be macrocycle size and
solvent type dependent [18,24,47]. And so, an analog of 1
13-membered hydroxyazobenzocrown C (Fig. 1) exists mainly in
quinone-hydrazone formandonlyinDMSOits azophenol tautomer
(30%) was observed. This probably affects the stability constant
values of hydroksyazobenzocrowns metal cation complexes.
They are lower than for their unsubstituted parent compounds
A and B (Fig. 1). It can be explained by tautomeric equilibrium
distribution, where stabilized by intermolecular hydrogen bond
quinone-hydrazone form is dominating. Aminoazobenzocrowns,
similarly to simple open-chain aminoazobenzene compounds [48],
preferably exist in aminoazo forms. This in turn can explain the
higher values of the stability constant of their metal cation com-
plexes. Tautomeric equilibrium of functionalized azobenzocrown
ethers is exemplied in Fig. 3 with 13-membered crowns.
The solvatochromism of aminoazobenzocrown 1 (see
Supplementary data, Fig. S1a) was also studied. In aprotic,
highly dipolar (non-hydrogen bond donor) solvents: acetonitrile,
DMSO and DMF spectra are similar in shape, but differ in their
intensity. In methylene chloride newband of a moderate intensity
appear at about 500nm. This band is better observable in protic
(HB) methanol. Excluding solvent affected tautomeric equilibrium,
it may be assumed that a band at 500nm in UVvis spectrum
is an effect of interactions between ligand and solvent, namely
intermolecular hydrogen bond formation resulting in possible
aggregation of azo compound. Observed spectral changes upon
water addition to acetonitrile solution of 1 (see Supplementary
data, Fig. S1b) can point interactions between azobenzocrown and
water molecules.
Acidbase properties of aromatic azo compounds make them
useful as potential pHindicators. Protonationof azobenzenemoiety
takes place at one of the two azo N-atoms [45]. Aminoazoben-
zenes are generally protonated both at amino and nitrogen atom
of azo group [46,48]. Protonation of aminoazobenzocrown 1 was
studied by spectroscopic methods in organic solvents. UVvis
titration with perchloric acid in acetonitrile results in the for-
mation of a new, intensive band at 483nm (see Supplementary
data, Fig. S2a). Color changes from yellow to orange. Clear
isosbestic point (414nm) and molar ratio plot (not shown)
suggest monoprotonation of compound 1. In
1
H NMR spec-
trum of 1 recorded in the presence of 1eq. of perchloric acid
in d-acetonitrile (see Supplementary data, Fig. S2b) aromatic
proton signals are shifted downeld and one N H proton signal is
observed at 13.6ppm.
1
H NMR spectrumrecorded in the presence
of 1eq. of perchloric acid in d-DMSOshows two signals at 9.4 and
one singlet at 13.4ppm. Similar changes were observed in
1
HNMR
spectrum1 in the presence of p-toluenesulfonic acid (TosOH) and
isolatedadduct of 1-TosOH(1:1) (seeSupplementarydata, Fig. S2b).
Those signals were also well observable in spectrum registered in
the presence of the excess of TosOH in d-chloroform. Observed
signals pattern can suggest stimulated by acids tautomeric equi-
libriumshifted toward protonated imino-hydrazone formof 1. The
scheme of reversible protonation of 1 is shown in Fig. S2d (see
Supplementary data).
Protonation of aromatic amides 3 and 4 causes color change
from yellow to pink-red. Color changes of 4 in the presence of
TosOH are illustrated in Fig. 4.
Most of azo compounds are nonuorescent at room temper-
ature; however, there are some exceptions reported in literature
[4953]. We found that protonated formof azobenzocrown ethers
is uorescent. The comparison of the normalized absorption and
uorescence spectra of protonated A, 1 and 3 are shown in
Fig. 5.
Changes in UVvis and uorescence spectrum upon titra-
tion of 4 with p-toluenesulfonic acid in acetonitrile are shown
in Fig. 6a and c. Fig. 6b and d illustrates color change and
red uorescence of ligand 4 in the presence of 2eqs. of
TosOH.
The reversible protonation of azobenzocrowns 14 causes red
uorescence with emission band over 600nm. The highest Stokes
shift is observed in a case of an unsubstituted azobenzocrown A
121nm, then for aromatic amide 3 and aromatic amine 1: 86 and
81nm, respectively.
Fig. 4. Color change of 4 (1.1210
3
M) solution in acetonitrile in the presence of
p-toluenesulfonic acid (TosOH). (For interpretation of the references to color in this
gure legend, the reader is referred to the web version of the article.)
E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923 917
400 450 500 550
0.0
0.2
0.4
0.6
0.8
1.0
N
o
r
m
a
l
i
z
e
d

a
b
s
o
r
b
a
n
c
e
nm
A
1
3
(a)
550 600 650 700
0.0
0.2
0.4
0.6
0.8
1.0
N
o
r
m
a
l
i
z
e
d

f
l
u
o
r
e
s
c
e
n
c
e
nm
A
1
3
(b)
Fig. 5. Normalized absorption spectra of protonated (TosOH, 2eq.) 13-membered azobenzocrowns A, 1 and 3 (a) and normalized uorescence spectra of A (zex =487nm,
zem =608nm), 1 (zex =482nm, zem =568nm) and 3 (zex =490nm, zem =576nm) (b) in acetonitrile.
3.3. Complexation studies in solution
3.3.1. Metal cation complexation
Alkali and alkaline earth metal cations (used as perchlorates)
binding was studied in acetonitrile by UVvis spectroscopy.
As a rst target, 13- and 16-membered aminoderivatives 1 and
2 and 16-membered aromatic amide 4 were chosen. As can be
expected, for 13-membered azobenzocrown 1 changes in absorp-
tion spectra were observed in the presence of lithiumperchlorate.
Changes upon titration of 1 with lithiumperchlorate are shown in
Fig. 7a. Sodiumand potassiumsalts did not inuence signicantly
the absorption spectrum. In comparison to the parent compound A
spectral changes upon lithiumcomplexation are more remarkable
for 1, although the stability constants values (logK, 1:1) of their
lithium complexes are comparable: 4.00 [9] for A and 4.01 for 1.
Azobenzocrown 1 in its spectral behavior resembles compound E
[18]. Among alkaline earth metal cations the most distinct spectral
changes for 1 were observed in the presence of magnesium per-
chlorate. Titration with magnesiumsalt results in the formation of
a new band at 482nm (^z=+99nm). Absorption spectrum, typ-
ically for azo compounds, is almost completely analogous to this
which is registered in acidic medium[48,54]. Moreover, longwave
band is still observable not only in the presence of neutral salt but
also in slightly basic solution in the presence of organic base (Et
3
N)
(see Supplementary data, Fig.S3). Additionof triethylamine to solu-
tion of 1 does not affect UVvis spectrum. Our studies suggest the
origin of the observed spectral behavior as ionligand interaction.
Amino derivative 1 preferably binds magnesium cation (being a
hard acid in HSAB theory) with stability constant (logK) 6.43. It
proves a benecial electron donating resonance effect of the amine
residue introduction into 13-membered azobenzocrown skeleton.
Fig. 7b shows the limiting absorption spectra obtained upon titra-
tion of 1 with alkaline earth metal salts. Fig. 7c illustrates titration
course for 1 and magnesiumperchlorate in acetonitrile. Addition-
ally, photos in Fig. 7 show selective color response of 1 toward
magnesiumcation.
Alkali and alkaline earth metal cations complexation was also
studied for 16-membered azobenzocrown ethers. The obtained
stability constant values for 16-membered azobenzocrowns 2
(amine), 4 (aromatic amide) and 16 (etheramide) and data avail-
able for the reference compounds are collected in Table 1.
In a case of 2, typically for 16-membered azobenzocrowns,
spectral changes (acetonitrile) were observed in the presence of
lithium, sodiumand potassiumsalts (see Supplementary data, Fig.
S4a). Titration course of 2 with lithiumand sodiumsalts illustrate
Fig. S4b and c. Spectral changes in the presence of alkali metal per-
chlorates are the most distinct for lithiumcation. The comparison
of the stability constant values of alkali metal cation complexes
with 16-membered azobenzocrown ether 2 (Table 1) with values
obtained for unsubstituted reference azobenzocrown B points that
amino derivative 2 forms more stable complexes with the studied
metal cations. Only in the case of larger potassiumcation this effect
is not observed. Higher values of the respective binding constant
canbeexplainedbyelectrondonatingresonanceeffect of theamino
group increasing electron density at nitrogen atomof an azo group
participating in metal cation binding.
Aminoazobenzocrown 2 forms stronger complexes with alka-
line earth metal cations than with lithium, sodiumand potassium.
Fig. 6. Changes in absorption spectrum upon titration of 4 (3.7310
5
M) with TosOH (a), color change of 4 in the presence of 2eq. TosOH (b), changes in uorescence
spectrum of 4 (3.7310
5
M) upon titration of 4 with TosOH (zex =510nm, zem =598nm) (c), uorescence of 4 in the presence of 2eq. TosOH (d) in acetonitrile. (For
interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)
918 E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923
Fig. 7. Spectral changes upon UVvis titration of 1 (3.2710
5
M) with lithiumperchlorate (a), the limiting spectra obtained during titration of 1 with alkaline earth metal
perchlorates (b), titration course for magnesiumperchlorate (c), in acetonitrile. Photos show color changes of solution of 1 in the presence of 1eq. of metal perchlorates in
acetonitrile. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of the article.)
Table 1
Comparison of the stability constant values of new16-membered azobenzocrown ethers 2, 4, 6 and the respective reference compounds in acetonitrile. By bold the highest
values of binding constants are marked.
Compound LogK
Li
LogKNa LogKK LogKMg LogK
Ca
LogK
Sr
LogKBa
2 5.33 5.04 2.90 6.06 6.40 6.13 6.32
4 4.82 4.60
a
3.47 5.30 5.87 6.00
16 3.58 3.61
a
4.99 5.96 6.32 6.26
B [10] 4.00 3.69 3.15 5.00 5.15 4.91 4.61
F [24] 4.28 4.75 3.74
a a a a
H [55] 4.18
a
3.34 4.02
a a a
a
No data or changes too small to estimate the stability constant value.
It is in agreement with the general trend observed for non-
substituted azobenzocrown ethers studied by Nakamura et al. [10],
but stability constant values are higher for aminoazobenzocrown
2 than for parent compound B (Fig. 1). Fig. 8a shows the limiting
spectra obtained during titration of 2 with alkaline earth metal
salts. Comparison of the spectrophotometric response of 1 and 2
in acetonitrile toward alkaline earth metal cations implies that
magnesium selectivity is determined by macrocyle size. Larger
16-membered aminoazobenzocrown does not showsuch selective
changes in absorption spectrumin the presence of magnesiumsalt.
InFig. 8bandc changes uponspectrophotometric titrationof 2with
magnesiumand bariumperchlorates are presented.
Complexing properties of 2 were compared to the cation bind-
ing ability of the aromatic amide 4 of the same ring size. For
4, among studied alkali metal cations, changes in absorption
spectrum were observed in the presence of lithium and sodium
salts (see Supplementary data, Fig. S5a). In Fig. S5b the respec-
tive limiting spectra obtained for alkaline earth metal cations are
shown. Opposite to16-memberedaminoazobenzocrown2less sig-
nicant and selective spectral changes were observed for aromatic
amide 4 in the presence of alkaline earth metal cations. Only in
the presence of magnesium cation the band shape is slighty dif-
ferent than in a case of other studied metal cations. Fig. S5c is an
example of spectral changes upon titration of 4 with metal cation
salts in acetonitrile and shows titration with calcium perchlo-
rate. For etheramide 16 spectral changes caused by the presence
of metal cations are similar to those, which were observed for
4. Stability constant values of its complexes are generally lower
than for 16-membered aminoazobenzocrown 2. Comparing to aro-
matic amide 4 etheramide 16 forms more stable complexes with
350 400 450 500 550 600
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
A
nm
free
Mg
Ca
Sr
Ba
(a)
350 400 450 500 550 600
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Mg
2+
= 0-8.3x10
-4
M
A
nm
(b)
350 400 450 500 550 600
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Ba
2+
= 0-8.2x10
-4
M
A
nm
(c)
Fig. 8. The limiting spectra obtained during titration of 2 (5.6210
5
M) with alkaline earth metal perchlorates (a), changes upon UVvis titration with magnesium(b) and
barium(c) perchlorates in acetonitrile.
E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923 919
250 300 350 400 450 500
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
A
nm
free
Li
Na
K
(a)
250 300 350 400 450 500
0.0
0.1
0.2
0.3
0.4
0.5
A
nm
free
Li
Na
K
(b)
A G 5 7 9
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
L
o
g

K
Azobenzocrown
(c)
Fig. 9. Spectral changes of azobenzocrowns: 9 (3.7510
5
M) (a), G (1.8410
5
M) (b) in the presence of 50-fold excess of alkali metal perchlorates, the comparison of the
stability constant values of lithiumcomplexes of azobenzocrowns A, G, 5, 7 and 9 (c) in acetonitrile.
alkaline earth metal cations, especially with strontium (Table 1).
Obtained results for 1, 2, 4 and 16 allow us to conclude that the
most promising sensor material for spectrophotometric detection
of metal cations, mainly magnesium, is 13-membered aminoa-
zobenzocrown 1. Metal cation recognition can be considered as an
acidbase interaction of hard acid with basic donor atoms: oxygen
of polyether chainandnitrogenatomof azo moiety. Ionrecognition
and the binding strength in studied azobenzocrowns are deter-
mined not only by the size of the macrocyle, but also by the type of
substituent in para position to an azo residue.
Alkali metal cations binding by selected oxyalkylenesters 510
was studiedinacetonitrile as a solvent. For 13-membered5, 7and9
differing inthe lengthof aliphatic linker (cf. Scheme 1), typically for
13-membered azobenzocrowns, the largest spectral changes were
observedfor lithium. Neglibleor nospectral changes wereobserved
in the presence of sodium and potassium salts. Spectral changes
caused by the presence of metal salts for oxyalkylenesters men-
tioned above are similar to alkoxy derivative G spectral behavior
[55]. In Fig. 9a and b spectra of 9 and G in the presence of 50-
fold excess of lithium perchlorate in acetonitrile are compared.
Fig. 9c shows stability constant values (logK) lithium complexes
of 13-membered oxyalkylenesters of different length of the acid
residue.
Earlier we have reported uorescence properties of pyrrole con-
taining azobenzocrowns [27]. Our preliminary tests showed that
not only acids, but also metal cations cause changes in uorescence
of someazobenzocrownethers presentedhere. Theseexperimental
studies are ongoing in our laboratory.
3.3.2. Anion binding testing
The presence of N H residue as amino and particularly as
amide function, cause that anionligand interactions being a
result of hydrogen bond formation between ion and ligand are
probable. Thus, the possibility of anion binding by the selected
macrocycles was also tested. Firstly, anionazobenzocrown ethers
interactions were studied with UVvis spectrophotometry in ace-
tonitrile. The studies were carried out for amino (1, 2) and
aromatic amide azobenzocrown 3 and 4. Among the studied anions
were halogenides, oxygen containing inorganic (hydrogen sul-
fate, dihydrogen phosphate, and perchlorate) and organic (acetate,
benzoate, and p-toluenesulfonate) anions used as their tetra-n-
butylammonium salts. Besides p-toluenesulfonates and hydrogen
sulfates no or not signicant spectral changes were found in the
presence of investigated anions. Spectra in the presence of hydro-
gen sulfate were not stable within the timescale of experiment. The
possible interaction with p-toluenesulfonate is hardly to evaluate
duetoextremelystrongresponseof theinvestigatedsensor materi-
als towardeventraces of acids. Inbasic environment, e.g. equimolar
to ligands amount of Et
3
N minimal changes in absorption spectra
caused by the presence of TBATos are observed.
3.4. Ion selective membrane electrodes
The ionophoric properties of functionalized azobenzocrown
ethers 310 and 1316 were investigated in classic ion selec-
tive membrane electrodes (ISEs). It was found that, etherester
and etheramide, behave similarly to described earlier alkyl and
dialkyl derivatives of 13- and16-memberedazobenzocrownethers
[11,12,18]. They are good ionophores in classic membrane elec-
trodes. Electrodes with 13-membered crowns as ionophores show
sodiumselectivity. Sensors with larger 16-membered ion-carriers
are potassiumsensitive when ionophore concentration in a mem-
brane is high enough. A driving force in this case seems to be
sandwich typecomplexes formationwiththemainions [20,22]. It
was found, that aromatic amides 3 and 4, in contrast to compounds
510 and 1316, are not good ionophores for ISE (long time needed
for electrodes conditioning, nonlinear characteristics, etc.)
Electrodes with 13-membered azobenzocrowns substituted in
para position to azo group as ionophores in membrane are more
pH sensitive than electrodes with membranes containing crowns
substituted in meta position. Thus preferentially potentiometric
measurements should be carried out in slightly basic solutions
(electrodes potential is more stable comparing to measurements
at neutral pH, selectivity coefcient logK
Na,K
is slightly better, but
differences in logK generally do not differ more than 0.1). The
main selectivity coefcients values (logK
Na/K
and logK
K/Na
) for
classic electrodes with PVC membranes containing 5% (w/w) of
ionophore and o-NPOE used as a plasticizer are collected in Table 2.
Selectivity coefcients logK
M,H
are also included. A signicant
change of selectivity coefcient logK
M,H
was found for electrodes
with changing of the macrocycle size of the ionophore. Electrodes
with 13-membered ion-carriers are more pH sensitive in relation
to main ion than those containing their 16-membered analogs. As
example, potentiometric response toward sodium, potassiumand
hydrogen cations for electrodes with membranes based on com-
pounds 9 and 10 as ionophores are shown in Fig. 10.
Because of the observed progress in sensor miniaturization we
decidedto use compounds 710 and1316 as ionophores inminia-
ture, planar, all solid state potentiometric sensors. Previously, we
have investigated the possibilities of bisazocrown ethers appli-
cation as ionophores in graphite screen printed electrodes [19].
Electrodes of this type are also used in the present studies. Com-
pounds 5 and 6 were excluded since their leakage from classic
electrode membranes. Membranes of similar composition as used
for classic ISE, but carbon nanotubes enriched, were poured onto
graphite screen-printed electrodes. Characteristics of the obtained
920 E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923
Table 2
The selectivity coefcients (logK
Na/K
, logK
Na/H
) or (logK
K/Na
, logK
K/H
) and slopes for classic ISE (PVC/o-NPOE) with membranes doped with functionalized azobenzocrowns
and their comparison with electrodes based on ether derivatives G and H.
Ionophore Slope (mV/dec) logK
Na/K
logK
Na/H
Ionophore Slope (mV/dec) logK
K/Na
logK
K/H
SSM(10
1
M) SSM(10
1
M)
G 58 2.2 1.8 H 59 3.1 1.0
5 57 2.2 1.1 6 54 3.3 1.8
7 58 2.3 1.5 8 58 3.3 1.8
9 56 2.3 1.5 10 58 3.2 1.7
13 57 2.3 1.2 14 55 3.1 1.9
15 58 2.5 1.6 16 55 3.3 1.4
Fig. 10. Potentiometric response toward sodium, potassiumand hydrogen cations for classic membrane electrodes based on 9 (a) and 10 (b) ionophores.
Table 3
Characteristics of the microfabricated membrane electrodes on screen printed graphite surface based on 7, 9, 13, 15 (for sodium) and 8, 10, 14, 16 (for potassium) ionophores.
Ionophore 7 9 13 15 8 10 14 16
Linear response range [loga] 5 to 1 4.5 to 1 4.6 to 1 5 to 1 5.9 to 1 5.2 to 1 5.8 to 1 6 to 1
Detection limit [loga] 5.5 4.8 5.1 5.2 6.2 5.7 6.2 6.3
Slope (mV/dec) 58.4 60.2 58.7 57.5 58.9 57.3 56.4 55.9
sensors, i.e. linear response range, detection limit and slope are
collected in Table 3.
The obtained potentiometric selectivity coefcient values
logK
Na,X
and logK
K,X
are shown in Fig. 11.
Generally, the obtained results for all solid state and classic elec-
trodes are comparable. Among 13-membered azobenzocrowns the
best selectivity coefcient logK
Na,K
=2.44 was found for micro-
fabricatedsensor withcompound15(withoxybutyramide residue)
as ionophore. In a case of electrodes with 16-membered azoben-
zocrown ethers as ion-carriers no clear relationship between the
nature of a side chain and the selectivity coefcient can be drawn
out. Typical value is logK
K,Na
=3.30.
Compounds 8 and 10 were also used as membrane com-
ponents for a glassy carbon (GC) electrodes [56], but in this
case bis(2-ethylhexyl)sebacate (DOS) and potassium tetrakis[3,5-
bis-triuoromethyl)phenyl] borate as a lipophilic salt were
components of the membrane.
3.5. X-ray structure of ligand 8 sodiumcomplex
Good quality single crystals were obtained and it was found
by X-ray study, that analogously to parent compound B, azoben-
zocrown 8 forms with sodium iodide complex of stoichiometry
1:1. Complex of the composition [Na(8trans)]I crystallizes in the
triclinic space group P

1. Details of data collection and structure

renement are given in Table 4. The content of the asymmetric
unit is shown in Fig. 12. The structure is ionic. Sodium cation
centers the 16-membered macrocyclic cavity. The coordination
polyhedron around the sodium ion is a pentagonal pyramid. The
sodiumion is coordinated by one nitrogen and four oxygen atoms
in the basal plane and an iodide anion in the apical position.
Table 4
Crystal and structure solution and renement data for [Na(8trans)]I.
Compound [Na(8trans)]I
Empirical formula C
24
H
30
IN
2
NaO7
Formula weight 608.39
Crystal system Triclinic
Space group P

1
Unit cell dimensions
a, 8.4253(3)
b, 10.4563(3)
c, 15.6545(5)
,

88.582(3)
,

87.169(3)
,

70.496(3)
V,
3
1298.35(8)
Z 2
D
calc
, Mg/m
3
1.556
, mm

1 1.30
F(000) 616
0 range for data collection,

2.428.5
Reections collected/unique 18,772/5644
Data/restraints/parameters 5644/0/317
GOOF on F
2
1.06
Final R indices [I >2o(I)], R
1
, wR
2
0.036, 0.086
Largest diff. peak and hole, e

A
3
1.21 and 0.52
E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923 921
Fig. 11. Potentiometric selectivity coefcient values, determined by SSMmethod (10
1
M) obtained for microfabricated electrodes based on screen printed graphite: logKNa,X
with 13-membered azobenzocrown ethers (a), logKK,X with 16-membered azobenzocrown ethers (b) as ionophores. Electrode numbers correspond to compound numbers.
Fig. 12. Viewof scorpion-like [Na(8trans)]I complex.
The NaO distances fall within the range 2.361(2)2.474(2)

A. The
N(1) nitrogen atom of the macrocyclic molecule coordinates to
the sodium atom at the distance of 2.502(3)

A, the Na(1)N(2)
separation till the distal nitrogen atom being 3.469

A, the iodide
anion which is completed the coordination polyhedron is at the
NaI separation of 3.0143(12)

A. Four oxygen and one nitrogen
atoms in the basal plane are coplanar within 0.24

A, the Na(1)
and N(2) atoms are displaced from this plane at 0.77 and 0.47

A,
respectively. The structure of the complex is quite similar to
[Na(Btrans)]I (where B=non-substituted 16-membered azocycle
[23] where NaOdistances are in the range 2.3902.464, NaNdis-
tances are 2.4552.481, NaI separation being 3.008

A). The torsion
angle C(1) N(1) N(2) C(13) equal to 179.2

indicates the trans

orientation of the aromatic substituents in 8. The ester side
chain is not involved in coordination to the metal center and
adopts an extended conformation. The conformations of the
16-membered macrocycle are quite similar for 8 and B as it
follows from comparison of torsion angles which differ only
by the C8 O2 C9 C10 and C9 C10 O3 C11 torsion angles
(see Table S1)
Two complex molecules related by an inversion center formthe
dimeric units via weak H I contact, H(17) I(1)* =3.11

Aand
stacking interactions between the partially overlapping aromatic
fragments, the centroid centroidseparationbeing of 4.20

A. Inthe
crystal complexes stack along the shortest a crystallographic axis
(Fig. S6).
4. Conclusions
New sensor materials: 13- and 16-membered azobenzocrown
ethers with aromatic amino, aromatic amide, etherester and
etheramide residue were obtained. Spectroscopic studies showed
that not only macrocyle size, but also the nature of the substituent
in benzene ring in para position to an azo group, i.e. aromatic
amine (1, 2) or aromatic amide (4) strongly inuences metal
cation selectivity and the stability constant values of their alkali
and alkaline earth metal complexes in acetonitrile. The respec-
tive values are in most cases higher than for parent compounds
A and B. 13-Membered aminoazobenzocrown shows magnesium
selective spectrophotometric response in acetonitrile. Magnesium
922 E. Wagner-Wysiecka et al. / Sensors and Actuators B 177 (2013) 913923
cation recognition is manifested by color change from yellow to
orange andlarge (99nm) spectral shift of the complex band. Large
spectral bands separation (100nm) and color change fromyellow
to orange or pink-red was found to be response of 14 for acids
in acetonitrile. Weakly uorescent azobenzocrowns 14 in their
protonated forms showcharacteristic red uorescence with Stokes
shift about 100nm.
Lariat derivatives: oxyalkylesters and oxyalkylamides are bet-
ter material for potentiometric than spectrophotometric sensors.
Azobenzocrowns studied here, analogously to 13-membered alkyl
and ether derivatives, are sodium selective ionophores in ISE,
whereas 16-membered crowns show potassium sensitivity. Men-
tioned ion carriers may be used in membranes of miniature all solid
state type electrode. The obtained results also showed the possibil-
ities of chemical connection of azobenzocrowns via ester or amide
bond with membrane components without loss of the selectivity.
16-Membered azobenzocrown 8 forms crystalline complex with
sodiumiodide(1:1) similarlytoreferencecompoundB. It explains
relatively large amounts of 16-membered crowns needed for elec-
trode membranes preparation what favors sandwich type complex
formation with potassium and in a consequence good potassium
selectivity of electrodes.
Acknowledgments
E. W-W. kindly acknowledges support fromSources for Science
grant no. N N204 137438 in years 20102011. Financial support
of this work from Gdansk University of Technology (DS grant no.
020223/003) is gratefully acknowledged. Authors thank MS stu-
dents for their experimental contribution.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2012.11.068.
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Biographies
Ewa Wagner-Wysiecka obtained her PhD in Chemistry at Gdansk University of
Technology (Poland) in 2002, where nowis working as assistant professor. The main
streamof her research is supramolecular chemistry, namely studies of the mecha-
nisms of molecular recognition. Currently the topic of the studies is design, synthesis
and studies of anion recognition by chromogenic and uorescent receptors.
Tomasz Rzymowski obtained his PhDin chemistry in 2012 after being PhDstudent
at Chemical Faculty of Gdansk University of Technology (Poland). His PhD thesis,
supervisor Prof. El zbieta Luboch, was entitled: Macrocycles with chromo- and/or
uoroionophoric nature.
MirosawSzarmach (MSc) is a PhD student at Chemical Faculty of Gdansk Univer-
sity of Technology (Poland). The topic of his PhD thesis under supervising of Prof.
El zbieta Luboch covers the synthesis of macrocyclic sensor materials for potentio-
metric sensors.
Marina S. Fonari obtained her PhD in crystallography and crystal physics at A.V.
Shubnikov Institute of Crystallography in 1992 (Moscow, Russia). Her scientic
interests cover X-ray crystallography of supramolecular and coordination com-
pounds, with an emphasis on weak interactions in molecular complexes based
on the crown ethers and crownophanes; crystallography of uorine-containing
compounds and complexes. She is leading scientic worker in Institute of Applied
Physics of the Academy of Sciences of Moldova.
El zbieta Luboch (PhD1983, DSc 2007) is currently a professor at Gdansk University
of Technology (Poland). The main topics of her scientic work are connected with
organic synthesis, organic supramolecular chemistry, chemical potentiometric sen-
sors and studies of correlation between structure and ionophoric properties of the
sensor materials. She is also interested in pharmaceutical chemistry (identication
of drug impurities, standard substances synthesis).