Unique hydrogen bonds between 9-anthracenyl hydrogen and anions

Article abstract of DOI:10.1021/jo049281+

Unique hydrogen bonds of the 9-H of anthracene moieties in hosts 1 and 2 with fluoride and pyrophosphate ions were observed on the basis of the ¹H NMR experiments. Furthermore, hosts 1 and 2 act as a colorimetric sensor and a fluorescent chemosensor for the recognition of fluoride ion, respectively.

Full text of DOI:10.1021/jo049281+

hydrogen bonds between the 9-H of anthracene with
fluoride and pyrophosphate ions are described on the
basis of the H NMR experiments.
Un iqu e Hyd r ogen Bon d s betw een
9-An th r a cen yl Hyd r ogen a n d An ion s
1
J i Young Kwon,† Yun J ung J ang,† Sook Kyung Kim,†
Keun-Hyeung Lee,‡ J ong Seung Kim,*,§ and
J uyoung Yoon*,†
Our synthesis began with 1,8-dinitroanthraquinone.
Modifying the published procedures,4 1,8-diaminoan-
thraquinone was obtained in a 73% yield. 1,8-Diami-
noanthracene was also synthesized following the pub-
lished procedure.5 Treating this diaminoanthracene or
1-aminoanthracene with p-nitrophenyl isocyanate in CH2-
Cl2 afforded 1 or 3 in 75% or 82% yield, respectively.
Application of similar procedures to phenylisocyanate
gave 2 and 4 in 80% and 85% yield, respectively (Figure
1).
Because of the low solubility of hosts 1-4, the NMR
data was obtained in DMSO-d6. Upon the addition of
anions, downfield shifts of the N-H protons were clearly
observed.
For example, upon addition of 4 equiv of chloride ions,
dramatic downfield shifts of the amide N-H peaks were
observed for hosts 1 (∆δ ) 1.71 ppm), 2 (∆δ ) 1.05 ppm),
3 (∆δ ) 1.86 ppm), and 4 (∆δ ) 0.85 ppm).
Recently, Lee et al. reported6 a strapped calix[4]pyrrole
in which not only four pyrrole hydrogens but also an
aromatic hydrogen in a strap form hydrogen bonds with
fluoride and chloride ion. These unique hydrogen bonds
between aromatic hydrogens and anions were confirmed
by the large downfield shifts of the aromatic hydrogens
(∆δ ) 0.41 for F-, 0.96 for Cl-).6a Other examples of
receptors in which aromatic hydrogens participate in
hydrogen bonding with anions have also been reported.7
A partial 1H NMR spectrum is shown in Figure 2, and
each peak was assigned based on the 2D COSY spectrum.
When tetrabutylammonium chloride was added to the
solution of 2, large downfield shifts of the amide N-H
bonds as well as 9-H of the anthracene moiety were
Department of Chemistry, Ewha Womans University,
11-1 Daehyon-Dong, Sodaemun-Ku, Seoul 120-750, Korea,
Department of Chemistry, Inha University, 253,
Yonghyeon-Dong, Nam-Ku, Incheon 402-751, Korea,
and Department of Chemistry, Dankook University,
Seoul 140-714, Korea
jyoon@ewha.ac.kr; jongskim@dankook.ac.kr
Received April 29, 2004
Abstr a ct: Unique hydrogen bonds of the 9-H of anthracene
moieties in hosts 1 and 2 with fluoride and pyrophosphate
ions were observed on the basis of the 1H NMR experiments.
Furthermore, hosts 1 and 2 act as a colorimetric sensor and
a fluorescent chemosensor for the recognition of fluoride ion,
respectively.
The recognition and sensing of anions has become the
focus of considerable attention1 because of the important
roles played by anions in biological, industrial, and
environmental processes. Of particular interest in this
regard are “colorimetric anion sensors” and “fluorescent
chemosensors for anions”. Recent efforts to investigate
anion binding by naked eye detection2 and through
fluorescent changes3 may provide important results.
We report herein on new colorimetric sensor and
fluorescent sensors for fluoride and pyrophosphate ions
in which two p-nitrophenylurea groups or two phenylurea
groups are immobilized on the 1,8-position of anthracene.
A new colorimetric sensor displays a unique color change
upon the addition of fluoride ions. Furthermore, unique
(3) (a) Yoon, J .; Kim, S. K.; Singh, N. J .; Lee, J . W.; Yang, Y. J .;
Chellappan, K.; Kim, K. S. J . Org. Chem. 2004, 69, 581. (b) Lee, J . Y.;
Cho, E. J .; Mukamel, S.; Nam, K. C. Org. Chem. 2004, 69, 943. (c)
Cho, E. J .; Moon, J . W.; Ko, S. W.; Lee, J . Y.; Kim, S. K.; Yoon, J .;
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M.; Mito-oka, Y.; Hamachi, I. J . Am. Chem. Soc. 2003, 125, 10184. (e)
Kim, S. K.; Singh, N. J .; Kim, S. J .; Kim, H. G.; Kim, J . K.; Lee, J . W.;
Kim, K. S.; Yoon, J . Org. Lett. 2003, 5, 2083. (f) Ojida, A.; Mito-oka,
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† Ewha Womans University.
‡ Inha University.
§ Dankook University.
(1) For recent reviews for anion receptors, see; (a) Martı´nez-Ma´n˜ez,
R.; Sanceno´n, F. Chem. Rev. 2003, 103, 4419. (b) McCleskey, S. C.;
Metzger, A.; Simmons, C. S.; Anslyn, E. V. Tetrahedron 2002, 58, 621.
(c) Beer, P. D.; Gale, P. A. Angew. Chem., Int. Ed. 2001, 40, 486.
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Res. 2001, 34, 963. (d) Snowden, T. S.; Anslyn, E. V. Chem. Biol. 1999,
3, 740. (e) Antonisse, M. M. G.; Reinhoudt, D. N. Chem. Commun. 1998,
143. (f) Schmidtchen, F. P.; Berger, M. Chem. Rev. 1997, 97, 1609. (g)
Rudkevich, D. M.; Brzozka, Z.; Palys, M.; Visser, H. C.; Verboom, W.;
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Int. Ed. 2002, 41, 3809. (d) Zhong, Z.; Anslyn, E. V J . Am. Chem. Soc.
2002, 124, 9014. (e) McCleskey, S. C.; Metzger, A.; Simmons, C. S.;
Anslyn, E. V. Tetrahedron 2002, 58, 621. (f) Piotr, P.; J anusz, J . Chem.
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10.1021/jo049281+ CCC: $27.50 © 2004 American Chemical Society
Published on Web 06/30/2004
J . Org. Chem. 2004, 69, 5155-5157
5155

F IGURE 1. Structures of compounds 1-4.
F IGURE 3. Partial 1H NMR (250 MHz) of 4 (1 mM) in DMSO-
d6 at 25 °C: (a) compound 4 only; (b) 4 + 1 equiv of
tetrabutylammonium fluoride; (c) 4 + 7 equiv of tris(tetrabu-
tylammonium) hydrogenpyrophosphate; (d) 4 + 10 equiv of
tetrabutylammonium chloride.
F IGURE 2. Partial 1H NMR (250 MHz) of 2 (1 mM) in DMSO-
d6 at 25 °C: (a) compound 2 only; (b) 2 + 1 equiv of
tetrabutylammonium fluoride; (c) 2 + 7 equiv of tris(tetrabu-
tylammonium) hydrogenpyrophosphate; (d) 2 + 10 equiv of
tetrabutylammonium chloride.
observed (Figure 2). On the other hand, when tris-
(tetrabutylammonium)hydrogen pyrophosphate or tet-
rabutylammonium fluoride were added to the solution
of 2 in DMSO-d6, four amide N-H signals as well as 9-H
in the anthracene moiety, displayed severe broadness.
We also observed a similar result with host 1. However,
hosts 3 and 4 only displayed this broadness of the amide
N-H peaks and large downfield shifts of the 9-H of
anthracene moiety when fluoride or pyrophosphate ions
were added (Figure 3). Along with the large downfield
shifts of the 9-H peaks of 1 and 2 obtained with Cl-, these
observations concerning the 1H NMR spectra obtained
with fluoride and pyrophosphate led us to the conclusion
that the 9-H of anthracene moiety formed a strong
hydrogen bond with the anions in DMSO. Hosts 1 and 2
have extremely rigid binding sites for anions and the 9-H
of anthracene moiety can participate in anion recognition
more efficiently than that in hosts 3 and 4.
F IGURE 4. Partial 1H NMR (400 MHz) of 2 (6 mM) in DMF-
d7 upon addition of tris(tetrabutylammonium) hydrogenpyro-
phosphate (7 equiv): (a) 25 °C, (b) 10 °C, (c) -5 °C, (d) -15
°C, (e) -30 °C.
The changes in color were studied in DMSO by the
addition of 300 equiv of the corresponding anions (F-,
H2PO4-, Cl-, Br-, I-, HSO4-, acetate, and pyrophosphate,
each added as their tetrabutylammonuim salts) to solu-
tions of host 1 (0.01 mM). There was a unique color
change from pale yellow to red when fluoride or pyro-
phosphate ions were added. Figure 5 illustrates the UV
absorption spectra of these experiments. Host 1 displays
unique new peaks (λmax ) 485 nm) with a red-shift of 129
nm upon the addition of fluoride or pyrophosphate ions.
It is worth mentioning that host 1 can easily differentiate
-
pyrophosphate from H2PO4 by naked eye detection.
Temperature-dependent 1H NMR studies in DMF-d7
are displayed in Figure 4. At -5 °C, the amide peaks as
well as 9-H of anthracene moiety concomitantly began
The unique color changes with F- and pyrophosphate
can be rationalized by three combined factors explained
previously by other reports. The excited state in a
complex can be more stabilized by anion binding, result-
ing in a bathochromic shift in the absorption maxima as
well as a color change.2a,i,j,8 The selective color changes
for F- and pyrophosphate can be rationalized on the basis
1
to appear in the partial H NMR spectrum of host 2 in
the presence of 7 equiv of pyrophosphate. Similar results
were observed in the presence of F- (see the Supporting
Information).
5156 J . Org. Chem., Vol. 69, No. 15, 2004

1
on the H NMR experiments. Furthermore, hosts 1 and
2 act as a colorimetric sensor and a fluorescent chemosen-
sor for the recognition of fluoride ion, respectively. The
anthracene moieties in hosts 1 and 2 act not only as a
fluorescent or colorimetric source but also as templates
for introducing the binding selectivity.
Exp er im en ta l Section
1,8-Bis(4-n itr oph en ylu r ea)an th r acen e (1). 1,8-Diaminoan-
thracene was prepared obtained from 1,8-diaminoanthraquino-
ne1 following the published procedure.2 A solution of 1,8-
diaminoanthracene (100 mg, 0.48 mmol) and 4-nitrophenyl
isocyanate (328 mg, 2.00 mmol) in dry CH2Cl2 (25 mL) was
refluxed for 2 h. As soon as 4-nitrophenyl isocyanate was added,
a white precipitate was formed. After cooling to room temper-
ature, the solid was filtered and washed with CHCl3. Analyti-
cally pure 1 was obtained in 75% yield (193 mg): mp 300 °C
1
dec; H NMR (DMSO-d6) δ 9.77 (s, 2H, NH), 9.16 (s, 2H, NH),
F IGURE 5. UV absorption changes of 1 (0.01 mM) upon
8.88 (s, 1H), 8.68 (s, 1H), 8.19 (d, 4H, J ) 9.2 Hz), 7.93 (d, 2H,
J ) 8.6 Hz), 7.84 (d, 2H, J ) 8.3 Hz), 7.74 (d, 4H, J ) 9.2 Hz),
7.55 (t, 2H, J ) 8.3 Hz); 13C NMR (DMSO-d6) δ 154.3, 152.8,
146.4, 141.1, 133.6, 131.8, 127.4, 125.7, 125.3, 124.3, 117.5, 115.3,
114.7; HRMS (FAB) m/z 537.1523 (M + H)+, calcd for C28H21N6O6
537.1523.
-
addition of the tetrabuthylammonium salt of H2PO4-, HSO4
CH3CO2-, Cl-, I-, Br-, PP, and F- (300 equiv) in DMSO.
,
of the guest basicity and the partial negative charge at
the 9-position of anthracene moiety which can be gener-
ated by a strong interaction between anion and 9-H of
anthracene. Recently, a naphthalene derivative bearing
two urea groups at the 1,8-position was reported to show
a unique absorption and fluorescent peak with fluoride
ion.3b,c In these reports, calculations suggested that the
increased anionic character of urea nitrogen due to the
strongly charged hydrogen bonding between fluoride and
amide protons of the urea can be the reason for this
observation.
For hosts 2 and 4, a fluorescence method made it
possible to readily follow their binding with anions. Upon
the addition of the tetrabutylammonium salts of anions
in DMSO, fluorescent quenching effects were observed
(see the Supporting Information). For example, from the
fluorescent titration experiments, the association con-
stants were calculated as being 108 000 (host 2 with F-),
9700 (host 2 with Br-), 6000 (host 2 with pyrophosphate),
4000 (host 4 with F-), and 2600 (host 4 with pyrophos-
phate) M-1, respectively (errors < 10%).9 There was not
any significant fluorescent change upon the addition of
up to 500 equiv of Br- to the solution of 4. The selectivity
for fluoride is around 100 times than that for bromide.
Furthermore, two urea groups in host 2 generate a better
binding site for anions than just one urea group in host
4, showing higher values (∼250 times) in its association
constants. Furthermore, these fluorescent data were
productively compared with UV data.
1,8-Bis(p h en ylu r ea )a n th r a cen e (2). Application of proce-
dure A to 100 mg of 1,8-diaminoanthracene (0.48 mmol) and 238
mg of phenyl isocyanate (2.00 mmol) in dry CH2Cl2 (25 mL) gave
202 mg of 2 (82% yield): mp 305 °C dec; 1H NMR (DMSO-d6) δ
9.11 (s, 2H, NH), 9.04 (s, 2H, NH), 8.92 (s, 1H), 8.63 (s, 1H),
7.92 (d, 2H, J ) 6.9 Hz), 7.84 (d, 2H, J ) 6.9 Hz), 7.54 (m, 6H),
7.32 (t, 4H, J ) 7.5 Hz), 7.01 (t, 2H, J ) 7.3 Hz); 13C NMR
(DMSO-d6) δ 153.1, 141.1, 134.2, 131.8, 128.9, 127.3, 125.8,
125.3, 123.1, 121.9, 118.2, 117.0, 114.0; HRMS (FAB) m/z
469.1610 (M + Na)+, calcd for C28H22N4O2Na 469.1640.
1-(4-Nitr op h en ylu r ea )a n th r a cen e (3). Application of pro-
cedure A to 100 mg of 1-aminoanthracene (0.52 mmol) and 344
mg of 4-nitrophenyl isocyanate (2.1 mmol) in dry CH2Cl2 (25 mL)
gave 149 mg of 3 (80% yield): mp 275-278 °C; 1H NMR (DMSO-
d6) δ 9.83 (s, 2H, NH), 9.18 (s, 2H, NH), 8.75 (s, 1H), 8.63 (s,
1H), 8.24 (d, 2H, J ) 9.2 Hz), 8.14 (m, 2H), 7.98 (d, 1H, J ) 7.0
Hz), 7.89 (d, 1H, J ) 7.0 Hz), 7.79 (d, 2H, J ) 9.2 Hz), 7.55 (m,
3H); 13C NMR (DMSO-d6) δ 152.6, 146.5, 141.1, 133.4, 131.88,
131.2, 131.0, 128.3, 127.9, 126.9, 126.2, 126.1, 125.6, 125.4, 125.3,
124.2, 120.1, 117.6, 117.2; HRMS (FAB) m/z 358.1196 (M + H)+,
calcd for C21H16N3O3 358.1192.
1-(P h en ylu r ea )a n th r a cen e (4). Application of procedure A
to 100 mg of 1-aminoanthracene (0.52 mmol) and 250 mg of
phenyl isocyanate (2.1 mmol) in dry CH2Cl2 (25 mL) gave 138
mg of 4 (85% yield): mp 282-285 °C; 1H NMR (DMSO-d6) δ
9.12 (s, 2H, NH), 8.96 (s, 2H, NH), 8.76 (s, 1H), 8.61 (s, 1H),
8.13 (m, 2H), 8.02 (d, 1H, J ) 7.4 Hz), 7.82 (d, 1H, J ) 7.4 Hz),
7.52 (m, 5H), 7.33 (t, 2H, J ) 7.4 Hz), 7.01 (d, 1H, J ) 7.3 Hz);
13C NMR (DMSO-d6) δ 152.6, 139.8, 134.1, 131.9, 131.1, 130.8,
128.9, 128.3, 127.9, 127.2, 126.7, 125.9, 125.6, 125.2, 123.1, 122.7,
121.9, 120.4, 119.8, 118.2, 118.0, 115.8; HRMS (FAB) m/z
312.1251, calcd for C21H16N2O 312.1263.
In conclusion, unique hydrogen bonds of the 9-H of
anthracene moieties in hosts 1 and 2 with fluoride and
pyrophosphate ions were observed in a first time based
Ack n ow led gm en t. This work was fully supported
by a Grant (No. 2002-042-C00045) from the Korea
Research Foundation.
(8) Nishizawa, S.; Kato, R.; Hayashita, T.; Teramae, N. Anal. Sci.
1998, 14, 595.
(9) (a) Conners, K. A. Binding Constants; Wiley: New York, 1987.
(b) Association constants were obtained using the computer program
ENZFITTER, available from Elsevier-BIOSOFT, 68 Hills Road, Cam-
bridge CB2 1LA, U.K..
Su p p or tin g In for m a tion Ava ila ble: The Experimental
Section, NMR spectra, and fluorescent spectra. This material
is available free of charge via the Internet at http://pubs.acs.org.
J O049281+
J . Org. Chem, Vol. 69, No. 15, 2004 5157