A voltammetric study of the chemosensor activity of aminoanthracene derivatives

Article abstract of DOI:10.1007/s11176-005-0509-2

The redox activity of potent chemosensors based on anthryl-containing diamines, thioureas, and ureas in the absence and in the presence of complexing metal cations in solution was studied by cyclic and differential pulse voltammetry. The free energy of in

Full text of DOI:10.1007/s11176-005-0509-2

Russian Journal of General Chemistry, Vol. 75, No. 11, 2005, pp. 1774 1781. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 11, 2005,
pp. 1857 1865.
Original Russian Text Copyright
2005 by Profatilova, Bumber, Tolpygin, Rybalkin, Gribanova, Mikhailov, Bren’.
A Voltammetric Study of the Chemosensor Activity
of Aminoanthracene Derivatives
I. A. Profatilova*, A. A. Bumber**, I. E. Tolpygin*, V. P. Rybalkin**,
T. N. Gribanova**, I. E. Mikhailov*, and V. A. Bren’**
*
Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
*
* Research Institute of Physical and Organic Chemistry, Rostov State University, Rostov-on-Don, Russia
Received November 1, 2004
Abstract The redox activity of potent chemosensors based on anthryl-containing diamines, thioureas,
and ureas in the absence and in the presence of complexing metal cations in solution was studied by cyclic
and differential pulse voltammetry. The free energy of intramolecular electron transfer was calculated. The
experimental conclusions were confirmed by ab initio RHF/6-31G** calculations. A correlation was found
between the electrochemical and photophysical data for the compounds studied.
0
Determination of traces of metals in various natural
objects became recently an urgent problem of environ-
mental studies. A new approach to solving this prob-
lem is the use of highly sensitive chemosensors
operating on the basis of the photoinduced electron
transfer (PET) effect [1, 2]. The essence of this effect
is as follows. In the absence of a substrate, photoexci-
tation of a chemosensor molecule consisting of a com-
plexing fragment, a signaling fragment, and a bridge
causes an intramolecular electron transfer from the
highest occupied molecular orbital (HOMO) of the
receptor to the vacant orbital of the fluorophore,
quenching the fluorophore fluorescence. When a cati-
on is bound, the receptor HOMO energy decreases,
its oxidation potential increases, the electron transfer
becomes more difficult, and the fluorescence of the
signaling fragment is observed. Anthracene and its
derivatives are often used as fluorophores.
electron acceptor, V; and G ( ), factor taking into
account the dielectric premeability of the solvent ( )
and the distance between the centers of the donor and
2
acceptor (a, ) and calculated as e /4 a, eV.
As investigation objects we chose potent chem-
osensors, anthryl-containing diamines, thioureas, and
ureas I XI, and also compounds modeling separate
fragments of the molecules under consideration:
9
-aminomethylanthracene XII, thiourea XIII, and
anthracene XIV.
Our goal was to determine the redox potentials of
potent chemosensors, calculate the free energy of
intramolecular electron transfer, and evaluate how
these quantities correlate with the photophysical data
reflecting the PET effect.
The synthesis of anthryl-containing derivatives I,
IV, and V was described elsewhere [6]. The com-
pounds were prepared along side Scheme 1.
If a chemosensor molecule contains electrophore
groups, its activity can be evaluated electrochemically.
This approach is based on a correlation between the
HOMO and LUMO (lowest unoccupied molecular
orbital) energies of a compound, on the one hand, and
electrochemical potentials of its oxidation and reduc-
tion, on the other hand [3].
The characteristics of the voltammograms of I XI
and of models XII XV, determined by differential
pulse voltammetry, are given in the table. The choice
of this method is governed by the high accuracy of
measuring the potentials in the case of reversible and
irreversible systems and good resolving power [7].
The data obtained are well consistent with the half-
peak redox potentials E1/2 determined by cyclic volt-
ammetry under the same conditions.
The free energy of electron transfer is estimated by
the Rehm Weller equation [4, 5]:
0
0
+ (E 0
0
0
G
=
E
+
E )
G ( ).
As seen from the table, compounds I XII are re-
duced under the experimental conditions, defined by
the presence of the anthryl fragment. The reduction
yields a stable radical anion and is characterized by a
reversible one-electron peak in the cathodic branch of
et
0 0
d /d
a/a
where E0 is the energy of the photoexcited state of
0
0
0
the fluorophore, eV; E
electron donor, V; E , reduction potential of the
+
, oxidation potential of the
d /d
0
a/a
1
070-3632/05/7511-1774 2005 Pleiades Publishing, Inc.

A VOLTAMMETRIC STUDY OF THE CHEMOSENSOR ACTIVITY
1775
Scheme 1.
H
N
H
N
H
O
1) n-BuOH;
) NaBH , EtOH DMFA
H
N
H
N
2
+
4
H
X
H
X
IV
S H
N
H
N
N
AlNCS, C H
6
6
PhNCS, C H
6 6
N
R
N R
H
S
VIII
V VII
PhCOCl, NH NCS,
4
p-ClC H NCO,
6 4
CH CN
3
C H
6 6
H
H
N
Cl
N
N
R
N
H
O
O
S
XI
IX, X
X = (CH ) (I), (CH ) (II), (CH ) (III), (CH ) (IV); R = H (V), CH C H (VI),
2
2
2 3
2 4
2 6
2 6 5
(
CH ) NHCH
(VII), H (IX), CH2C6H5 (X).
2
2
2
the voltammogram (Fig. 1). The potential of this peak
in most cases is close to that of unsubstituted anthra-
cene XIV [8]. It is known that substituted aliphatic
amines give no reduction waves on solid and mercury
dropping electrodes [9]. The thioamide group (with
thiourea used as model) did not undergo cathodic re-
duction under the experimental conditions (see table).
An additional evidence of the assumption that the
reduction involves primarily the anthryl fragment is
the LUMO localization on this fragment, according to
quantum-chemical calculations.
The peaks in the anodic branch of the voltammo-
grams at 0.95 1.05 V (e.g., signal A, Fig. 1) corre-
spond to the electrooxidation of the receptors of the
compounds whose potentials were taken into account
0
el
in the subsequent calculations of G . This is con-
firmed by published data on oxidation of aliphatic
amines in acetonitrile [10] and of urea derivatives [3],
and also by the closeness to the values of the oxida-
tion potentials of model compounds XII and XIII.
Oxidation of these donor fragments is irreversible; an
unstable radical cation is formed in the first step,
which is followed by a fast chemical reaction.
Oxidation of the compounds under consideration
occurs in one or two steps involving the anthryl frag-
ment and the donor moiety (amino, thiourea, or urea
group). Generally the anodic process corresponds to
the ECEC mechanism (E, electrochemciial reaction;
C, chemical reaction) [3] for two-step oxidation and
EC mechanism for one-step oxidation.
As seen from the table, for I X the second oxida-
tion step is observed. As judged from the potentials
and shape of the signals, this is the anodic branch of
the anthryl fragment. It is known that anthracene is
reversibly oxidized via formation of a stable radical
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

1776
PROFATILOVA et al.
Redox potentials of compounds and complexes on platinum disk electrode in acetonitrile vs. saturated calomel electrode,
calculated Gibbs energies of the electron transfer, and relative intensities of the fluorescence
Ligand
Complex
Comp.
no.
Cation
H+
0
0
Ep.c, V
Ep.a, V
g , eV
I0
Ep.c, V
Ep.a, V
g , eV
I/I0
et
et
I
1.85
1.00
0.25
0.32
0.29
0.22
5.2
2.05
2.00
1.35
1.30
>>0
0.20
32.0
42.0
2
+
+
+
+
1
.05
Zn
1
.45
II
1.85
1.88
1.83
0.93
.58
1.0
4.1
7.4
H+
Zn
2.05
2.00
1.35
1.25
>>0
0.15
15.0
10.0
2
1
1
.48
III
IV
0.93
.50
H+
Zn
2.00
2.00
1.38
1.13
>>0
0.03
64.0
2.5
2
1
1
.50
1.05
.50
H+
Zn
2.10
2.00
1.38
1.10
>>0
0.18
36.0
26.0
2
1
1
.28
V
1.98
1.45
1.95
1.98
1.98
2.07
0.98
1.00
0.14
0.65
0.20
0.17
0.07
0.03
27.6
1.9
Hg2+
Hg2+
H+
1.83
2.25
>>0
2.5
1
1.03
.43
VI
VII
VIII
IX
X
0.18
77.0
1
.38
0.95
.40
0.95
.30
1.05
.50
1.00
.63
5.9
2.08
1.98
1.95
1.15
1.30
1.15
0.13
0.18
0.00
13.0
12.0
11.0
2
+
1
Zn
Hg
2
+
11.8
142.9
138.9
1
Cu2+
H+
2.08
1.00
0.02
0.8
1
2.28
2.05
1.88
2.13
1.05
0.93
1.35
1.20
0.23
0.12
0.11
0.8
0.9
11.7
2.2
2
+
1
Co
Hg
2
+
XI
XII
1.85
1.90
0.98
1.10
0.27
0.10
4.1
125.4
+
H
>>0
1
.45
XIII
XIV
XV
0.94
1.35
0.38
1.98
a
XII, 9-aminomethylanthracene; XIII, thiourea; XIV, anthracene; XV, ferrocene.
0
cation in the first step [8]. The nature of the subse-
quent chemical steps was not examined.
oxidation and G . Generally, the free energy of the
el
electron transfer is determined by the difference be-
tween the redox potentials of the donor and acceptor
in the molecule and by their mutual electronic effects.
It should be noted that the PET effect is the strongest
for VI, and with this compound the increase in the
Similar oxidation pattern was reported for chemo-
sensors, 9,10-bis(1,3-dithiol-2-ylidine)-9,10-dihydro-
anthracene derivatives, in which the sulfur-containing
ionophore was oxidized at about 0.35 V, and the oxi-
dation peak of the anthracene moiety was observed at
2+
relative fluorescence intensity in the presence of Hg
ions is the most pronounced (see table). The low
1
.62 V (vs. Ag/AgCl) [11].
absolute value of G0 for IX and X may be due to
el
The experimentally determined redox potentials
the presence of the electronegative chlorine atom
decreasing the donor power of the receptor.
0
were subsequently used for calculating
G
by the
el
above equation. For I XII, we observed a small PET
effect compared to systems in which both electron
donors and acceptors are aromatic [12]. There is no
apparent correlation between the ease of the donor
We found an empirical correlation between the free
energies of electron transfer (electrochemical param-
eters) and relative fluorescence intensities (photophys-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

A VOLTAMMETRIC STUDY OF THE CHEMOSENSOR ACTIVITY
ical data). Theoretically, the stronger the PET effect,
1777
the more efficient should be the intramolecular fluo-
rescence quenching and the lower should be the fluo-
rescence intensity, which is reflected in Fig. 2. As
seen, an exponential dependence is observed.
B
2
25 A
A
In the second part of our study, we examined the
redox behavior of the compounds in acetonitrile solu-
tion on adding cations. We considered cations whose
coordination caused the most significant changes in
1
the relative fluorescence intensity (see I/I values in
0
the table).
1
0
1
2 E, V
+
The electrochemical pattern changed on adding H ,
2
+
2+
2+
2+
Fig. 1. Differential pulse voltammogram of oxidation
reduction of II in acetonitrile (1) in the absence and
Zn , Hg , Cu , and Co ions (table, Fig. 1), owing
to protonation or complexation. For the complexes,
the peak potentials are given in the table for the anth-
ryl fragment.
2
+
(
0
2) in the presence of Zn ions. Supporting electrolyte
.1 M tetraethylammonium perchlorate. (A and B) are the
signals oxidation of amino groups and anthryl fragment
Upon protonation of the amino groups in I IV and
XII, only the oxidation peak of the anthryl fragment
was observed at sweeping anodic potential within the
in II, respectively.
log I0
2.5
working potential range; the parameters of this peak
0
el
were not taken into account in the calculation of G .
It is known that tetrasubstituted amines undergo elec-
trooxidation at potentials higher than 2 V vs. saturated
calomel electrode.
2
1
1
.0
.5
.0
The table shows that in most cases, as expected,
the photoinduced electron transfer becomes thermo-
dynamically unfavorable in the presence of cations,
2
+
except the complexes of IX and X with Cu and
2
+
Co . Apparently, in these complexes the electron is
transferred from the central metal atom to the fluoro-
phore; such cases were described in the literature [12].
To interpret theoretically the effects of intramolec-
ular electron transfer examined electrochemically, we
analyzed in this study the orbital interactions in di-
amines I III and compound VI. The efficiency of
various intra- and intermolecular interactions is largely
determined by the efficiency of orbital ionteractions in
this molecular system and can be qualitatively esti-
mated by molecular-orbital analysis.
0
.5
0
0
.6
0.4
0.2
0
0
G
, eV
el
Fig. 2. Empirical correlation between the calculated free
energies of intramolecular electron transfer and photo-
physical data (logarithms of relative fluorescence inten-
sities) for I XII.
The calculations showed that diamines I III can
exist in the form of various cisoid and transoid con-
formers differing in the energy by no more than
1
2
kcal mol . The most stable complexes with metal
cations, according to quantum-chemical calculations,
are formed by the conformers shown in Fig. 3.
the HOMOs of the donor fragment of the diamines are
the orbitals of the lone electron pairs of the nitrogen
centers, and LUMO of the acceptor fragment is the
orbital of the anthracene moiety. The shapes of the
corresponding orbitals of diamine I are shown in
Fig. 4a; similar topology of the frontier orbitals of the
donor and acceptor fragments is characteristic of
diamines II and III.
The efficiency of orbital interactions determining
the transfer of the electron density from the donor
(
amino group) to acceptor (anthracene substituent)
fragment is detfined by the width of the energy gap
between the frontier orbitals of the fragment and by
their overlap integral. According to the calculations,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

1778
PROFATILOVA et al.
1.444N
1.518
1.454
1
.519
1
.449
N 1.457
N
1.519
1
.522
N
1
.452
1
.522
1.450
1
.453
1
.448
1
.533
1
.529
I
II
1
.520
1
.524
N 1.451
1.473
1
.455
N
1
.464
1
.358
1
.453
1.519
1.426
1
1
.453
.535
N
N
1
.528
1.353
1
.687
S
1
.535
III
VI
Fig. 3. Geometric characteristics of I III and VI, according to ab initio RHF/6-31G** calculations (bond lengths in ).
An NBO analysis [13] of the electronic structure of
electron donation compared to I and III, which is con-
firmed by the experimental data (see table).
diamines I III shows that the efficiency of donation
of the electron density from the lone electron pairs of
the nitrogen centers to the anthracene fragment is very
low (the energies of the corresponding orbital interac-
In the case of VI, HOMO of the donor fragment is
the orbital of the lone electron pair of the S atom, and
LUMO of the accceptor fragment, as in I III, is the
orbital of the anthracene fragment (Fig. 4b). In VI,
according to the calculations, the HOMO level of the
donor fragment and the LUMO level of the acceptor
fragment are appreciably closer ( EHOMO LUMO
1
tions do not exceed 1 kcal mol ), which is confirmed
by the experimental conclusion that the free energies
of intramolecular electron transfer in these systems are
low in absolute values. The low efficiency of the
intramolecular donor acceptor interaction is caused by
the large energy gap between the HOMO level of the
donor fragment and LUMO level of the acceptor frag-
ment ( EHOMO LUMO): According to RHF/6-31G**
calculations, EHOMO LUMO for diamines I III is
approximately the same, 11.6 eV. More favorable
orientation of the interacting orbitals in II provides
increased overlap integral and higher efficiency of the
9
.6 eV), which accounts for the experimentally
observed increase in the absolute value of the free
energy of the intramolecular electron transfer in VI
(
see table). Structure and some geometric param-
eters of VI are shown in Fig. 3.
Thus, we demonstrated the possibility of using
voltammetric methods for evaluating the chemosensor
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

A VOLTAMMETRIC STUDY OF THE CHEMOSENSOR ACTIVITY
1779
(
a)
LUMOacceptor
HOMOdonor
(
b)
LUMOacceptor
HOMOdonor
Fig. 4. Shapes of HOMO of the donor fragment and LUMO of the acceptor fragment in (a) I and (b) VI.
activity of anthryl-containing derivatives I XI. Their
electrochemical properties in acetonitrile were studied.
From the potential difference for the first anodic and
first cathodic redox transitions, associated with the
relative arrangement and energies of the frontier orbi-
tals, we calculated the free energy of the intramolecu-
lar electron transfer. We found that the compounds
show a small PET effect (from 0.03 to 0.65 eV),
which, however, allows them to be considered as
Cyclic and differential pulse voltammograms were
recorded by standard procedures [14, 15] in acetoni-
trile containing 10 3 M water with a platinum disk
electrode 2 mm in diameter, saturated calomel refer-
ence electrode, and platinum wire as auxiliary elec-
trode; the supporting electrolyte was 0.1 M tetraethyl-
ammonium perchlorate. The concentrations of the
3
compounds tested were 5 10 M, and those of the
2
cations added, 5 10 M; electrochemical measure-
+
2+
2+
promising chemosensors for H , Zn , and Hg ions.
The experimental data were confirmed by quantum-
chemical calculations.
ments were performed under Ar.
The voltammograms were taken on a PA-2 polaro-
graph equipped with a two-coordinate recorder; the
1
potential sweeping rate was 0.5 V s in cyclic volt-
EXPERIMENTAL
ammetry and 0.005 V s 1 in differential pulse voltam-
metry, at a pulse amplitude of 12.5 mV.
The IR spectra were recorded on a Specord IR-75
1
Quantum-chemical calculations were performed by
the ab initio RHF/6-31G** method [16] using the
GAMESS program [17]. The geometries of the mo-
spectrophotometer (mulls in mineral oil). The H
NMR spectra were taken on a Varian Unity-300 spec-
trometer (300 MHz), external reference TMS. The
electronic absorption spectra were measured on a
Specord M-40 spectrometer, and the fluoresence spec-
tra, on a Hitachi-650-60 spectrofluorimeter in aceto-
nitrile. The melting points were determined in glass
capillaries with a PTP(M) device.
lecular structures were optimized to a gradient of
4
10
Hartree/Bohr; the stationary points were identi-
fied by calculating the force constant matrix.
N,N -Bis(9-anthrylmethyl)alkanediamines II
and III (general procedure). A 4.12-g portion of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

1780
PROFATILOVA et al.
1
1
9-anthraldehyde was dissolved in 50 ml of ethanol,
IR spectrum, , cm : 1607, 1475, 1315. H NMR
and 10 mmol of appropriate diamine and 0.5 ml of
glacial acetic acid were added. The mixture was
heated to reflux and cooled. The precipitate was fil-
tered off, washed with hot ethanol, dried in air, and
recrystallized from 1-butanol DMF, 2 : 1. Bisazo-
methines were obtained in a quantitative yield.
spectrum (DMSO-d ), , ppm: 1.9 2.1 m (2H, CH ),
6
2
3.41 3.55 m (2H, CH ), 4.0 s (2H, CH ), 6.28 s (2H,
2
2
CH ), 6.45 8.82 m (23H arom.). Found, %: C 81.3;
2
H 5.7; N 7.3; S 5.7. C H N S. Calculated, %: C
3
9
33
3
81.3; H 5.8; N 7.3; S 5.6.
N-Allyl-N -(9-anthrylmethyl)-N -benzylthiourea
VIII. A mixture of 0.6 g of N-(9-anthrylmethyl)-N-
benzylamine and 0.22 ml of allyl isothiocyanate in
10 ml of benzene was heated on a water bath for 2 h
and then cooled. The precipitate was filtered off,
washed with petroleum ether, and dried in air. Yield
A 1.9-g portion of finely divided NaBH was
4
added with stirring over a period of 2 h to a suspen-
sion of 5 mmol of azomethine in 100 ml of ethanol
DMF, 3 : 1, heated to 60 70 C. The mixture was
stirred at 60 70 C for an additional 2 h, the solution
was diluted with a twofold volume of water, and
excess borohydride was decomposed with dilute
67%, mp 140 141 C (1-butanol). IR spectrum,
,
1
1
cm : 3290, 1450, 1375. H NMR spectrum (DMSO-
d ), , ppm: 4.25 4.4 m (4H, 2CH ), 4.83 5.05 d.d
CH COOH. The precipitate was filtered off, dried,
3
6
2
and recrystallized from 1-butanol.
(2H, CH =), 5.55 t (1H, NH), 5.65 5.85 m (1H,
2
CH=), 6.38 s (2H, CH ), 6.75 8.5 m (14H arom.).
2
N,N -Bis(9-anthrylmethyl)propane-1,3-diamine
II. Yield 71%, mp 112 113 C (1-butanol). IR spec-
Found, %: C 78.6; H 6.2; N 7.1; S 8.1. C H N S.
2
6
24
2
1
1
Calculated, %: C 78.7; H 6.1; N 7.1; S 8.1.
trum, , cm : 1340, 1270. H NMR spectrum
DMSO-d ), , ppm: 1.78 t (2H, CH ), 2.92 t (4H,
N-(9-Anthrylmethyl)-N -(4-chlorophenyl)urea
IX. A 0.82-g portion of 9-aminomethylanthracene XII
was dissolved in 20 ml of benzene, and 0.48 ml of
phenyl isocyanate was added. The mixture was heated
for 15 min; the precipitate was filtered off, washed
with benzene, and dried in air. Yield 87%, mp
>325 C (sublimes, 1-butanol DMF). IR spectrum, ,
6
2
CH ), 4.61 s (2H, CH ), 7.3 8.5 m (18H arom.).
2 2
3
3
30
2
1
1
1
1
cm : 3300, 1627, 1555, 1464. H NMR spectrum
DMSO-d ), , ppm: 5.3 d (2H, CH ), 6.52 t (1H,
2 2
(
6
2
CH ), 4.7 s (4H, 2CH ), 7.3 8.6 m (18H arom.).
2 2
NH), 7.05 8.6 m (14H, arom. + NH). Found, %: C
3
4
32
2
7
%
3.1; H 4.7; Cl 9.7; N 7.8. C H ClN O. Calculated,
: C 73.2; H 4.8; Cl 9.8; N 7.8.
22 17 2
N-(9-Anthrylmethyl-N-R-N -phenylthioureas VI
and VII (general procedure). A 0.26-ml portion of
phenyl isothiocyanate was added to a solution of
N-(9-Anthrylmethyl)-N-benzyl-N -(4-chlorophen-
yl)urea X was prepared starting from N-(9-anthryl-
methyl)-N-benzylamine and phenyl isocyanate, as
described above for the synthesis of IX. Yield 77%,
2
mmol of appropriate amine in 30 ml of benzene.
The mixture was heated on a water bath for 2 h. The
precipitate was filtered off, washed with petroleum
ether, recrystallized from appropriate solvent, and
dried in air.
1
mp 174 175 C (1-butanol). IR spectrum, , cm :
1
3
287, 1625, 1460, 1367. H NMR spectrum (DMSO-
d ), , ppm: 4.24 s (2H, CH ), 5.81 s (2H, CH ), 6.33
6
2
2
s (1H, NH), 6.87 8.5 m (18H atom.). Found, %: C
77.2; H 5.1; Cl 7.7; N 6.2. C H ClN O. Calculated,
N-(9-Anthrylmethyl)-N-benzyl-N -phenylthio-
urea VI was prepared starting from N-(9-anthryl-
methyl)-N-benzylamine [12] and phenyl isothiocya-
nate. Yield 85%, mp 181 182 C (1-butanol). IR spec-
2
9
23
2
%: C 77.2; H 5.1; Cl 7.9; N 6.2.
N-(9-Anthrylmethyl)-N -benzoylthiourea XI.
A 0.55-g portion of ammonium thiocyanate was dis-
solved in 15 ml of absolute acetonitrile, 0.56 ml of
benzoyl chloride was added, and the mixture was
heated to reflux and left for 10 15 min. After that,
a solution of 0.83 g of amine XII in 5 ml of absolute
1
1
trum, , cm : 3320, 1455, 1378, 1305. H NMR
spectrum (DMSO-d6), , ppm: 4.56 s (2H, CH2),
6
.17 s (2H, CH ), 6.88 8.6 m (19H arom.), 9.46 s
2
(
1H, NH). Found, %: C 80.5; H 5.7; N 6.5; S 7.3.
C H N S. Calculated, %: C 80.5; H 5.6; N 6.5;
2
9
24
2
CH CN was added; the mixture was stirred, heated to
3
S 7.4.
reflux, and left at room temperature for 30 min. The
resulting mixture was poured into 50 ml of water; the
precipitate was filtered off, washed with water, and
dried in a vacuum desiccator over P O . Yield 74%,
N-(9-Anthrylmethyl)-N-[2-(9-anthrylmethyl-
amino)-ethyl]-N -phenylthiourea VII was prepared
starting from amine XII and phenyl isothiocyanate.
Yield 87%, mp 202 203 C (1-butanol DMF, 2 : 1).
2
5
1
mp 186 187 C (1-butanol). IR spectrum, , cm :
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005

A VOLTAMMETRIC STUDY OF THE CHEMOSENSOR ACTIVITY
1781
1
3
200, 1650, 1385. H NMR spectrum (DMSO-d ), ,
cheskoi khimii (Polarographic Methods in Analytical
6
ppm: 5.83 d (2H, CH ), 7.28 8.57 m (14H arom.),
Chemistry), Moscow: Khimiya, 1983.
2
9
7
.06 s (1H, NH), 10.83 s (1H, NH). Found, %: C
4.6; H 4.8; N 7.6; S 8.6. C H N OS. Calculated,
8
9
. Mann, C.K. and Barnes, K.K., Electrochemical Reac-
tions in Nonaqueous Solutions, New York: Dekker,
2
3
18
2
%
: C 74.6; H 4.9; N 7.6; S 8.6.
-Aminomethylanthracene XII was prepared by
the published procedure [18].
1
970. Translated under the title Elektrokhimicheskie
reaktsii v nevodnykh sistemakh, Moscow: Khimiya,
974, pp. 44, 109.
9
1
. Mairanovskii, S.G., Stradyn’, Ya.P., and Bezug-
ACKNOWLEDGMENTS
lyi, V.D., Polyarografiya v organicheskoi khimii
(
Polarography in Organic Chemistry), Leningrad:
The study was financially supported by CRDF (pro-
ject no. RO-004-X2), President’s Program for Support
of Scientific Schools (project no. NSh 945.2003.3),
and BRHE 2003 Post-Doctoral Fellowship Program of
CRDF and Ministry of Education (Y1-C-04-03).
Khimiya, 1975.
10. Mann, C.K., Anal. Chem., 1964, vol. 36, no. 13,
p. 2424.
1
1. Bryce, M.R., Batsanov, A.S., Finn, T., Hansen, T.K.,
Howard, A.K., Kamenjicki, M., Lednev, I.K., and
Asher, S.A., Chem. Commun., 2000, no. 4, p. 295.
REFERENCES
1
1
1
2. Fabbrizzi, L., Licchelli, M., Pallavicini, P., and Ta-
glietti, A., Inorg. Chem., 1996, vol. 35, no. 6, p. 1733.
1
. De Silva, A.P., Fox, D.B., Huxley, A.J.M., and
Moody, T.S., Coord. Chem. Rev., 2000, vol. 205,
p. 41.
3. Reed, A.E., Curtiss, Z.A., and Weinhold, F., Chem.
Rev., 1988, vol. 88, no. 6, p. 899.
4. Lukova, G.V., Bumber, A.A., Burlov, A.S., Olekhno-
2
3
. Bren’, V.A., Usp. Khim., 2001, vol. 70, no. 12,
p. 1152.
vich, E.P., and Garnovskii, A.D., Zh. Obshch. Khim.,
1
998, vol. 68, no. 4, p. 637.
. Organic Electrochemistry. An Introduction and a
Guide, Baizer, M.M. and Lund, H., Eds., New York:
Marcel Dekker, 1983. Translated under the title
Organicheskaya elektrokhimiya, Moscow: Khimiya,
1
1
1
5. Bumber, A.A., Lalakulich, O.D., Shibaeva, N.V.,
Kletskii, M.E., and Pyshchev, A.I., Khim. Geterotsikl.
Soedin., 1999, no. 1, p. 71.
6. Foresman, J.B. and Frisch, E., Exploring Chemistry
with Electronic Structure Methods, Pittsburgh:
Gaussian, 1996.
1
988, vol. 1, pp. 54, 79, 507.
4
5
. Adv. Phys. Org. Chem., 1982, vol. 18, p. 130.
. De Silva, S.A., Zavaleta, A., Baron, D.E., Allam, O.,
Isidor, E.V., Kashimura, N., and Percaprio, I.M.,
Tetrahedron Lett., 1997, vol. 38, no. 13, p. 2237.
7. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., El-
bert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, S.J., Windus, L.,
Dupuis, M., and Montgomery, A., J. Comput. Chem.,
1993, vol. 14, no. 11, p. 1347.
6
7
. Tolpygin, I.E., Bren’, V.A., Dubonosov, A.D., Min-
kin, V.I., and Rybalkin, V.P., Zh. Org. Khim., 2003,
vol. 39, no. 9, p. 1435.
1
8. Kristian, P., Zavodska, E., Antos, K., and Drob-
. Bond, A.M., Polyarograficheskie metody v analiti-
nica, L., Chem. Zvesti, 1967, vol. 21, nos. 1 2, p. 57.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 11 2005