A new colorimetric anion sensor which have both a fat brown RR dye and a nitrophenyl group as signaling group

Article abstract of DOI:10.1007/s10847-010-9813-5

A new colorimetric anion sensor 1 has been synthesized based on both Fat brown RR dye and a nitrophenyl group. This new receptor 1 could recognize the presence of fluoride and acetate ion selectively by the change of color of solution.

Full text of DOI:10.1007/s10847-010-9813-5

J Incl Phenom Macrocycl Chem (2011) 69:57–61
DOI 10.1007/s10847-010-9813-5
ORIGINAL ARTICLE
A new colorimetric anion sensor which have both a fat brown RR
dye and a nitrophenyl group as signaling group
•
Jin Joo Park Jongmin Kang
Received: 1 April 2010 / Accepted: 27 May 2010 / Published online: 11 June 2010
Ó Springer Science+Business Media B.V. 2010
Abstract A new colorimetric anion sensor 1 has been
synthesized based on both Fat brown RR dye and a nitro-
phenyl group. This new receptor 1 could recognize the
presence of fluoride and acetate ion selectively by the
change of color of solution.
As a part of our efforts to develop more efficient anion
receptors, we planned to design a new colorimetric anion
sensor 1 utilizing both Fat brown RR dye and nitrophenyl
group as chromogenic signaling sites and amide moiety as
binding sites. The receptor 1 was found to be an efficient
detector for fluoride ion by the change of UV–vis, 1H NMR
spectra and the naked-eye observation. Receptors 1 was
synthesized using the one step reaction of Fat Brown RR
and 4-nitrobenzoyl chloride in 76.3% yield (Scheme 1).1
The receptor 1 displayed strong absorption bands at
412 nm in DMSO. Figure 1a shows the family of spectra
obtained over the course of the titration of the solution 1 with
tetrabutylammonium fluoride in DMSO. As tetrabutylam-
monium fluoride was added to the 40 lM solution of 1, the
intensity of absorption spectrum decreased at 337 nm and
increased at 412 nm and the clear isosbestic point appears at
371 nm. This result suggests that a typical hydrogen bonding
complex forms between the receptor 1 and the fluoride ion as
the basicity of anion is insufficient to induce deprotonation of
receptor at this fluoride concentration. However, when an
excess of fluoride ions was added, a new intense absorption
band developed at 531 nm, which is attributed to the
deprotonated receptor [32].
Keywords Anion receptor Á Colorimetric receptor Á
Hydrogen bonding Á Naked eye detector
The rational design and synthesis of efficient receptors to
selectively recognize biologically and environmentally
important anion species is an attractive field of supramolec-
ular chemistry [1–7]. Both fluorogenic [8–15] and chromo-
genic [16–25] anion receptors have attracted a considerable
amount of attention due to the simplicity in recording their
optical responses upon forming complexes with anions.
For sensing approach, anion recognition site is usually
coupled to the reporting groups, which binding process is
transduced into a signaling event. The interaction with
anion typically stabilizes the excited state of chromophore
and induces red shift of the charge transfer absorption
band, thus providing an efficient way for qualitative and
quantitative evaluation of anion activity in solution [26]. In
addition, they can be often easily synthesized from com-
mercially available reagents even by a single step proce-
dure [27–29]. We have also reported on novel colorimetric
receptors containing a nitrophenyl group as chromogenic
signaling subunit and urea as binding sites, which were
selective for fluoride or acetate ion [30, 31].
In addition, spectra showed a new isosbestic point at
444 nm (Fig. 1b). The presence of the sharp isosbestic
point at 444 nm indicates that only two species were
1
To a solution of 200 mg (0.76 mmol) of Fat Brown RR in 10 mL of
dichloromethane was added 420 mg (2.26 mmol) of 4-nitrobenzoyl
chloride and the mixture was stirred overnight at room temperature.
The solvent was evaporated from the reaction mixture. Washing the
remained solid with acetone gave 326 mg of red solid in 76.3% yield.
1H NMR (DMSO-d6) 11.0 (d, J = 8.0, 2H), 8.9 (d, J = 9.0, 1H),
8.8 (s, 1H), 8.4 (m, 4H), 8.3 (q, J = 8.5, 4H), 8.1 (d, J = 8.0, 1H), 8.0
(m, 2H), 7.9 (m, 2H), 7.7 (m, 3H) LRMS (ES) calculated for
C30H20N6O6, 560.52; found for 560.57.
J. J. Park Á J. Kang (&)
Department of Chemistry, Sejong University, Seoul 143-747,
Korea
e-mail: kangjm@sejong.ac.kr
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J Incl Phenom Macrocycl Chem (2011) 69:57–61
Scheme 1 The synthetic
scheme for the anion receptor 1
O
N
NO2
O
CH2Cl2
76.3%
N
N
NH2 + O2N
N
N
Cl
O
H
H2N
N
H
1
Fat Brown RR
O2N
Fig. 1 Family of spectra
recorded over the course of
titration of 40 lM DMSO
solution of the receptor 1 with a
standard solution
tetrabutylammonium fluoride a
0–2 equivalents of fluoride ions
added b 0–25 equivalents of
fluoride ions added
present at equilibrium over the course of the titration
experiment. Therefore, fluoride ion initially forms the
hydrogen bonded complex, but with high excess of added
anions, the deprotonation occurs with formation of the
hydrogen bonded anion dimer F2H- (Fig. 2) [33]. The
deprotonated receptor 1 can be seen clearly when the
solution of the receptor 1 is titrated with tetrabutylammo-
nium hydroxide (Fig. 3). Like in the case of excess fluoride
ions with the receptor 1, absorption band at 531 nm
developed again.
Assuming 1:1 stoichiometry, a Benesi–Hildebrand plot
[34] by use of change in the 412 and 531 nm gave asso-
ciation constant and equilibrium constant for deprotonation
respectively. From the experiments, the receptor 1 showed
association constant 1.8 9 104 and equilibrium constant
8.3 9 102 for fluoride.
1
The binding phenomenon could be confirmed by a H
NMR titration in DMSO-d6 (Fig. 4). As the amide N–H
hydrogen peak became invisible upon addition of fluoride
ion, one of the aromatic signals located next to amide
Fig. 2 The interaction of
receptor 1 and fluoride
O
NO2
N
O
NO2
N
N
N
F-
O
N
N
H
N
O
H
F-
N
H
H
Yellow
O2N
O2N
O
NO2
N
N
N
H
F-
F2H-
O
+
N
_
Red
O2N
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J Incl Phenom Macrocycl Chem (2011) 69:57–61
59
excess acetate, the deprotonation occurs again (Fig. 5b).
The association constant and the equilibrium constant were
calculated as 8.5 9 103 and 2.7 9 102 respectively. In a 1H
NMR titration in DMSO-d6, the amide N–H hydrogen peak
became invisible upon addition of acetate ion and aromatic
signal at 8.40 ppm moved to 8.37 ppm and the saturation
occurred at 2.1 equivalents of acetate ions. The association
constant was calculated as 9.0 9 103, which is also similar
value obtained from UV–vis titration.
We also investigated association constants of other
anions. Among the anions investigated benzoate showed
only discrete hydrogen-bonded complex. Even with excess
benzoate ions, UV–vis spectra did not show any spectrum
result from deprotonation. Benzoate is not basic enough to
deprotonate the amide N–H hydrogen of the receptor 1 at
any concentration in DMSO. The association constant was
calculated as 1.5 9 103. Other anions such as chloride,
bromide, iodide, perchlorate, hydrogensulfate, nitrate did
not bind to the receptor 1 in DMSO at all.
Fig. 3 Family of spectra recorded over the course of titration of
40 lM DMSO solution of the receptor 1 with a standard solution
tetrabutylammonium hydroxide
(8.40 ppm) was used for titration. For the receptor 1, this
aromatic signal moved from 8.40 to 8.31 ppm until 1.5
equivalents of fluoride ion was added. In fact, two effects
are expected as a result of hydrogen bond formation
between the amide subunit and the anion. (i) A through-
bond propagation increases electron density in the phenyl
ring, which causes a shielding effect and promotes an
upfield shift (ii) A through-space effect increases a polar-
ization of C–H bonds, which causes deshielding and pro-
motes a downfield shift. In this case, the through-bond
propagation dominates, and an upfield shift is observed for
the all of aromatic peaks. Analysis of chemical shift uti-
lizing EQNMR [35] gave association constant 1.9 9 104,
which is similar value obtained from UV–vis titration.
With acetate, same phenomenon was observed. In
UV–vis titration, until 7 equivalents of acetate was added,
only hydrogen bonded complex forms (Fig. 5a). With
Figure 6 shows the color change of the solutions of the
receptor 1 upon additions of various anions in DMSO. It
can be seen that the color changed from yellow to red in the
presence of fluoride and acetate with naked eye. Other
anions did not induce any color changes even with excess
amounts. Probably, as we can see from the NMR titration
with fluoride ion, deprotonation of the receptor 1 by the
fluoride and acetate induces the change of the color.
In summary, we developed a new chromogenic anion
receptor 1 with utilizing Fat Brown RR and nitrophenyl
group as signaling group. The receptor 1 binds anions via
[
hydrogen bonds with a selectivity of F- [ CH3CO2
C6H5CO2 and proved to be an efficient naked-eye
-
-
detector for the fluoride and acetate ion.
Fig. 4 1H NMR spectra of
2 mM solution of 1 with
increased amounts of
tetrabutylammonium fluoride in
DMSO-d6
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J Incl Phenom Macrocycl Chem (2011) 69:57–61
Fig. 5 Family of spectra
recorded over the course of
titration of 40 lM DMSO
solution of the receptor 1 with a
standard solution
tetrabutylammonium acetate a
0–7 equivalents of acetate ions
added b 0–300 equivalents of
fluoride ions added
Fig. 6 The color changes of the receptor 1 when 40 lM solution of the receptor was treated with 20 equivalents of various anions in DMSO
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