N,N'-Bis(9-anthrylmethyl)diamines as fluorescent chemosensors for transition metal cations

Article abstract of DOI:10.1134/S1070428007030098

N,N'-Bis(9-anthryl)-substituted diamines, imidazolidines, and hexahydropyrimidines were synthesized, and their luminescence properties and complexing ability were studied. N,N'-Bis(9-anthrylmethyl)ethane-1,2-diamine and N,N'-bis(9-anthrylmethyl)butane-1,4-diamine were found to be effective and selective PET chemosensors for Zn²⁺ and H⁺, respectively. 2-[1,3-Bis(9-anthrylmethyl)hexahydropyrimidin-2-yl]-6-methoxyphenol can be used as fluorescent chemosensor for mercury(II) cations. Nauka/Interperiodica 2007.

Full text of DOI:10.1134/S1070428007030098

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 3, pp. 388–392. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © I.E. Tolpygin, V.P. Rybalkin, E.N. Shepelenko, N.I. Makarova, A.V. Metelitsa, Yu.V. Revinskii, A.V. Tsukanov, A.D. Dubonosov,
V.A. Bren’, V.I. Minkin, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 3, pp. 390–394.
N,N'-Bis(9-anthrylmethyl)diamines as Fluorescent Chemosensors
for Transition Metal Cations
I. E. Tolpygina, V. P. Rybalkinb, E. N. Shepelenkob, N. I. Makarovaa, A. V. Metelitsaa,
Yu. V. Revinskiia, A. V. Tsukanova, A. D. Dubonosovb, V. A. Bren’a, b, and V. I. Minkin a, b
a Institute of Physical and Organic Chemistry, Rostov State University, pr. Stachki 194/2, Rostov-on-Don, 344090, Russia
e-mail: dubon@ipoc.rsu.ru
b South Research Center, Russian Academy of Sciences, Rostov-on-Don, Russia
Received June 10, 2006
Abstract—N,N'-Bis(9-anthryl)-substituted diamines, imidazolidines, and hexahydropyrimidines were synthe-
sized, and their luminescence properties and complexing ability were studied. N,N'-Bis(9-anthrylmethyl)-
ethane-1,2-diamine and N,N'-bis(9-anthrylmethyl)butane-1,4-diamine were found to be effective and selective
PET chemosensors for Zn2+ and H+, respectively. 2-[1,3-Bis(9-anthrylmethyl)hexahydropyrimidin-2-yl]-6-
methoxyphenol can be used as fluorescent chemosensor for mercury(II) cations.
DOI: 10.1134/S1070428007030098
responsible for complex formation [9–19]. The 9-an-
thryl signaling fragment frequently plays the role of
fluorophore in chemosensor molecules [17, 18, 20–
23]; nevertheless, no detailed studies on luminescence
and complexing properties of the representative series
of diamines I–IX were performed so far.
We previously showed that N,N'-disubstituted di-
amines can be used as chemosensors for zinc cations
[1]. The results of DFT (B3LYP/LanL2DZ) quantum-
chemical calculations of N,N'-bis(9-anthrylmethyl)-
ethane-1,2-diamine as an example showed that the
energy of complex formation decreases in the series
Zn2+ > Hg2+ > Cd2+ due to joint action of steric and
orbital factors [2]. With a view to perform a detailed
study on the interaction of chemosensors of that type
with transition metal cations we synthesized N,N'-bis-
(9-anthrylmethyl)-substituted diamines I–V and prod-
ucts of their cyclization by the action of salicylalde-
hydes, N,N'-bis(9-anthrylmethyl)imidazolidines VI
and VII and N,N'-bis(9-anthrylmethyl)hexahydro-
pyrimidines VIII and IX (Scheme 1).
The electronic absorption spectra of compounds I–
IX contained a long-wave maximum in the region
λ 320–400 nm with a fine vibrational structure typical
of anthracene derivatives. The intensity of these bands
is twice as large as that intrinsic to model N-(9-anthryl-
methyl)phenylmethanamine having only one anthra-
cene fragment. Therefore, compounds I–IX can be
regarded as bichromophore systems in which the an-
thracene fragments do not interact with each other in
the ground state.
Compounds I–IX have a three-module structure
typical of PET (photoinduced electron transfer) chemo-
sensors [3–8]: their molecules contain a fluorophore
(anthracene fragment), receptor (amino groups), and
spacer (methylene bridge). Such systems give rise to
photoinduced electron transfer from the receptor to
fluorophore, which leads to considerable (or in some
cases complete) suppression of fluorescence. Addition
of a metal cation to the receptor of a chemosensor
makes PET unfavorable from the viewpoint of energy,
and fluorescence intensity appreciably increases. It
should be noted that in most cases polyamine-based
systems are widely used as chemosensor fragments
Photoexcitation of molecules I–IX at 293 K leads
to a weak emission in a broad range from 390 to
550 nm. The fluorescence band has a complex shape; it
shows a vibrational structure typical of local anthra-
cene emission (λ 390–450 nm) and a diffuse structure-
less emission in the λ range from 460 to 550 nm with
its maximum at λ 480 nm. The fluorescence excitation
spectra in the regions of 400 and 480 nm are identical,
and they coincide with the long-wave absorption of
compounds I–IX, indicating similar initial excited
states for the different emission bands. Presumably,
the fluorescence band of compounds I–IX at λ 460–
388

N,N'-BIS(9-ANTHRYLMETHYL)DIAMINES AS FLUORESCENT CHEMOSENSORS
389
Scheme 1.
CHO
(1) BuOH
(2) NaBH4, EtOH–DMF
X
H
N
H
N
+
H2N
NH2
X
I–V
R3
N
N
OH
R1
CHO
R2
VI, VII
OH
R1
I–III
+
R2
N
N
OH
R1
R2
VIII, IX
I, X = (CH2)2; II, X = CH(Me)CH2; III, X = (CH2)3; IV, X = (CH2)4; V, X = (CH2)6; VI, R1 = R3 = H, R2 = Me; VII, R1 = H,
R2 = R3 = Me; VIII, R1 = H, R2 = Me; IX, R1 = MeO, R2 = H.
series, shows almost no sensor activity toward zinc
cations (I/I0 = 2.6) but is the most sensitive to pH.
Insofar as no analytical signal necessary for deter-
mination of the composition of complexes formed was
550 nm corresponds to the interaction between the two
anthracene fragments with formation of intramolecular
excimer [24–27], and the position of its emission max-
imum (λ 480 nm) suggests that the anthracene frag-
ments are overlapped through one benzene ring [24].
Complex formation with various metal cations
strongly affects the thermodynamic parameters of
photoinduced electron transfer via binding of lone
electron pair on the nitrogen atom; as a result, the
fluorescence intensity changes, and compounds I–V
acquire sensor properties. Addition of bivalent transi-
tion metal acetates (Cu, Hg) to a solution of I–V in
acetonitrile induces a small attenuation of the anthra-
cene local emission, while addition of Zn2+ ions
strongly increases the fluorescence intensity (Fig. 1).
I/I0
– I
– II
60
– III
– IV
50
40
30
20
10
0
– V
H+
Zn2+
Cd2+
Cu2+
Hg2+
Compounds I and II in neutral medium are highly
efficient fluorescent chemosensors for Zn2+ ions, while
diamine IV, unlike the other members of the examined
Fig. 1. Relative increase in the fluorescence intensity of di-
amines I–V in acetonitrile (c = 5×10–5 M) upon addition of
metal cations (c = 2.5×10–4 M); λ 390 nm.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 3 2007

TOLPYGIN et al.
390
Ifl
6
7
VI–IX turned out to be less selective for transition
metal cations (Fig. 4), except for compound IX which
is a selective sensor for Hg2+ ions.
140
120
100
80
8
5
Thus our results showed that N,N'-bis(9-anthryl-
methyl)ethane-1,2-diamine (I) and N,N'-bis(9-anthryl-
methyl)butane-1,4-diamine (IV) are efficient and
selective PET chemosensors for Zn2+ and H+ ions,
respectively, and that 2-[1,3-bis(9-anthrylmethyl)hexa-
hydropyrimidin-2-yl]-6-methoxyphenol (IX) may be
used as fluorescent chemosensor for mercury(II) ions.
9
4
10
3
2
60
EXPERIMENTAL
1
40
1
The H NMR spectra were recorded on a Varian
Unity-300 spectrometer (300 MHz); the chemical
shifts were measured relative to signals from residual
protons in the deuterated solvent (CDCl3, δ 7.25 ppm;
DMSO-d6, δ 2.50 ppm). The electronic absorption
spectra were recorded on a Specord M-40 spectro-
photometer. The luminescence spectra were measured
on Hitachi 650-60 and Varian Eclipse spectrofluori-
meters. The IR spectra were obtained on a Specord
75IR instrument from samples dispersed in mineral oil.
The melting points were determined in glass capillaries
using a PTP (M) melting point apparatus. The progress
of reactions and the purity of products were monitored
by thin-layer chromatography on Silufol UV-254
plates using chloroform as eluent; development with
iodine vapor in a moist chamber.
20
0
400
450
500
λ, nm
Fig. 2. Plot of the fluorescence intensity of compound III in
acetonitrile (λexcit 365 nm) versus mole fraction of Zn(OAc)2 ·
2 H2O (c = 2 ×10–5 M). Curves 1–10 correspond to mole
fractions of Zn2+ from 0 to 0.9 through a step of 0.1.
observed in the electronic absorption spectra of com-
pounds I–V, the stoichiometry of their complex forma-
tion with Zn2+ ions was established by measuring the
fluorescence of their isomolar solutions (Fig. 2). The
isomolar diagram (Fig. 3) indicates that the composi-
tion of the resulting complex is 1:1 [1 mol of diamine
III per mole of Zn(OAc)2 ·2H2O]. Cyclic diamines
N,N'-Bis(9-anthrylmethyl)ethane-1,2-diamine (I)
and N,N'-bis(9-anthrylmethyl)hexane-1,6-diamine (V)
were synthesized previously [1].
Ifl
140
N,N'-Bis(9-anthrylmethyl)propane-1,2-diamine
(II) was prepared according to the procedure described
in [1] from anthracene-9-carbaldehyde and propane-
1,2-diamine. Yield 69%, mp 147–148°C (from butan-
1-ol). IR spectrum, ν, cm–1: 1465, 1370. 1H NMR spec-
trum (CDCl3), δ, ppm: 1.27 d (3H, CH3, J = 6.2 Hz),
2.70–3.22 m (3H, CH, CH2), 4.55–4.88 m (4H, CH2),
7.16–8.43 m (20H, Harom, NH). Found, %: C 87.00;
H 6.71; N 6.29. C33H30N2. Calculated, %: C 87.19;
H 6.65; N 6.16.
120
100
80
60
40
20
0
N,N'-Bis(9-anthrylmethyl)propane-1,3-diamine
(III) was prepared in a similar way [1] from anthra-
cene-9-carbaldehyde and propane-1,3-diamine. Yield
71%, mp 112–113°C (from butan-1-ol); published data
[24]: mp 109–110°C. IR spectrum, ν, cm–1: 3405,
1465, 1367. 1H NMR spectrum (CDCl3), δ, ppm: 1.78 t
(2H, CH2, J = 6.3 Hz), 2.92 t (4H, CH2, J = 6.6 Hz),
0.0
0.2
0.4
0.6
0.8
1.0
Mole fraction of Zn2+
Fig. 3. Isomolar diagram for the determination of the
composition of the complex formed by compound III with
zinc(II) acetate [dependence of the fluorescence intensity
of compound III in acetonitrile upon mole fraction of
Zn(OAc)2 ·2H2O, c = 2×10–5 M; λexcit 365 nm, λfl 390 nm].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 3 2007

N,N'-BIS(9-ANTHRYLMETHYL)DIAMINES AS FLUORESCENT CHEMOSENSORS
I/I0
391
– VI
4.61 s (4H, CH2), 7.31–8.49 m (18H, Harom). Found, %:
35
30
25
20
15
10
5
– VII
– VIII
– IX
C 87.11; H 6.73; N 6.12. C33H30N2. Calculated, %:
C 87.19; H 6.65; N 6.16.
N,N'-Bis(9-anthrylmethyl)butane-1,4-diamine
(IV) was prepared in a similar way [1] from anthra-
cene-9-carbaldehyde and butane-1,4-diamine. Yield
85%, mp 120–121°C (from butan-1-ol). IR spectrum,
1
ν, cm–1: 1465, 1367. H NMR spectrum (CDCl3), δ,
ppm: 1.65 s [4H, (CH2)2], 2.92 s (4H, CH2), 4.71 s
(4H, CH2), 7.33–8.62 m (18H, Harom). Found, %:
C 87.05; H 6.94; N 6.10. C34H32N2. Calculated, %:
C 87.14; H 6.88; N 5.98.
0
H+
Zn2+
Cd2+
Cu2+
Hg2+
Fig. 4. Relative increase in the fluorescence intensity of
compounds VI–IX in acetonitrile (c = 5×10–5 M) upon addi-
tion of metal cations (c = 2.5×10–4 M); λ 390 nm.
Compounds VI–IX (general procedure). A solu-
tion of 2 mmol of diamine I, II, or III and 2 mmol of
the corresponding substituted salicylaldehyde in 10 ml
of butan-1-ol (or benzene) was heated for 15–20 min
in the presence of an acid catalyst (acetic acid or
p-toluenesulfonic acid). The solvent was removed
under reduced pressure, and the precipitate was filtered
off, washed with petroleum ether, dried in air, and
recrystallized from butan-1-ol.
4.22 s (1H, CH), 4.50 d.d (4H, CH2, J1 = 38.8, J2 =
12.7 Hz), 6.69–8.62 m (21H, Harom), 9.80 s (1H, OH).
Found, %: C 86.02; H 6.39; N 4.91. C41H36N2O. Cal-
culated, %: C 85.98; H 6.34; N 4.89.
2-[1,3-Bis(9-anthrylmethyl)hexahydropyrimidin-
2-yl]-6-methoxyphenol (IX) was synthesized from
diamine III and 2-hydroxy-3-methoxybenzaldehyde.
Yield 68%, mp 260–261°C. IR spectrum, ν, cm–1:
2-[1,3-Bis(9-anthrylmethyl)imidazolidin-2-yl]-5-
methylphenol (VI) was synthesized from diamine I
and 2-hydroxy-4-methylbenzaldehyde. Yield 75%,
mp 219–220°C. IR spectrum, ν, cm–1: 1645, 1600,
1
1630, 1465, 1485. H NMR spectrum (DMSO-d6), δ,
ppm: 1.11–1.65 m (2H, CH2), 2.22–2.57 m (4H, CH2),
4.08 s (3H, CH3), 4.32 s (1H, CH), 4.48 d.d (4H, CH2,
J1 = 57.3, J2 = 12.8 Hz), 6.86–8.6 m (21H, Harom),
10.0 s (1H, OH). Found, %: C 83.49; H 6.35; N 4.80.
C41H36N2O2. Calculated, %: C 83.36; H 6.48; N 4.74.
1
1465, 1390. H NMR spectrum (DMSO-d6), δ, ppm:
2.41 s (3H, CH3), 2.44–2.78 m [4H, (CH2)2], 4.45 s
(1H, CH), 4.65 d.d (4H, CH2, J1 = 29.0, J2 = 12.7 Hz),
6.68–8.51 m (21H, Harom), 10.12 s (1H, OH). Found,
%: C 85.87; H 6.18; N 4.96. C40H34N2O. Calculated,
%: C 85.99; H 6.13; N 5.01.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 05-03-32470), by the Ministry of Education and
Science of the Russian Federation (project nos. RNP.-
2.2.2.2.5592, RNP.2.1.1.4939, RNP.2.2.2.3.9720), by
the CRDF (grant nos. REC-004/BP1M04, REC-004/
BF5M04), and by the Program of the Earth Science
Division of the Russian Academy of Sciences “Devel-
opment of Monitoring Technology, Ecosystem Model-
ing, and Predictions while Studying Natural Resources
under Arid Climate Conditions.”
2-[1,3-Bis(9-anthrylmethyl)-4-methylimidazoli-
din-2-yl]-5-methylphenol (VII) was synthesized from
diamine II and 2-hydroxy-4-methylbenzaldehyde.
Yield 72%, mp 259–260°C. IR spectrum, ν, cm–1:
1
1640, 1600, 1470, 1380. H NMR spectrum
(DMSO-d6), δ, ppm: 0.13 d (3H, CH3, J = 6.4 Hz),
2.17 d.d (2H, CH2, J1 = 9.1, J2 = 2.3 Hz), 2.44 s (3H,
CH3), 2.89 t (2H, CH2, J = 8.8 Hz), 3.07–3.24 m (1H,
CH), 4.33–4.67 m (3H, CH2, CH), 4.80 d.d (2H, CH2,
J1 = 22.4, J2 = 13.0 Hz), 6.61–8.42 m (21H, Harom),
10.22 s (1H, OH). Found, %: C 86.13; H 6.30; N 4.93.
C41H36N2O. Calculated, %: C 85.98; H 6.34; N 4.89.
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