1,3-Bis(pyren-1-yliminomethyl)calix[4]arene as a selective fluorescent turn-on sensor for mercury(II) ion

Article abstract of DOI:10.1080/10610278.2017.1388510

A novel calixarene-based diimine, 1,3-bis(pyren-1-yliminomethyl)calix[4]arene (5), serves as a turn-on-type fluorescent sensor, which selectively detects Hg²⁺ in THF/H₂O (99:1, v/v) in the presence of various other metal ions. Such selectivity is not seen with half salen 1 derived from salicylaldehyde and 1-aminopyrene. ¹H NMR analysis reveals that it is a chemodosimetric sensor based on its hydrolysis mediated by Hg²⁺ to release 1-aminopyrene molecules as fluorescent chromophores.

Full text of DOI:10.1080/10610278.2017.1388510

Supramolecular Chemistry
ISSN: 1061-0278 (Print) 1029-0478 (Online) Journal homepage: http://www.tandfonline.com/loi/gsch20
1,3-Bis(pyren-1-yliminomethyl)calix[4]arene
as a selective fluorescent turn-on sensor for
mercury(II) ion
Shinya Tanaka, Kengo Hirasawa, Kyohei Watanabe & Tetsutaro Hattori
To cite this article: Shinya Tanaka, Kengo Hirasawa, Kyohei Watanabe & Tetsutaro Hattori
(2017): 1,3-Bis(pyren-1-yliminomethyl)calix[4]arene as a selective fluorescent turn-on sensor for
mercury(II) ion, Supramolecular Chemistry, DOI: 10.1080/10610278.2017.1388510
To link to this article: http://dx.doi.org/10.1080/10610278.2017.1388510
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Date: 13 October 2017, At: 04:13

Supramolecular chemiStry, 2017
ꢁꢁꢂs://dꢃꢄ.ꢃꢅg/10.1080/10610278.2017.1388510
ꢀ
1
,3-Bis(pyren-1-yliminomethyl)calix[4]arene as a selective fluorescent turn-on
sensor for mercury(II) ion
Shinya Tanaka, Kengo Hirasawa, Kyohei Watanabe and Tetsutaro Hattori
Dꢆꢂꢇꢅꢁꢈꢆnꢁ ꢃf Bꢄꢃꢈꢃꢉꢆꢊꢋꢉꢇꢅ engꢄnꢆꢆꢅꢄng, Gꢅꢇdꢋꢇꢁꢆ Sꢊꢀꢃꢃꢉ ꢃf engꢄnꢆꢆꢅꢄng, tꢃꢀꢃkꢋ unꢄvꢆꢅsꢄꢁꢌ, Sꢆndꢇꢄ, Jꢇꢂꢇn
ABSTRACT
ARTICLE HISTORY
A novel calixarene-based diimine, 1,3-bis(pyren-1-yliminomethyl)calix[4]arene (5), serves as a turn-
rꢆꢊꢆꢄvꢆd 28 Jꢋꢉꢌ 2017
aꢊꢊꢆꢂꢁꢆd 29 Sꢆꢂꢁꢆꢈbꢆꢅ 2017
on-type fluorescent sensor, which selectively detects Hg2 in THF/H O (99:1, v/v) in the presence of
+
2
various other metal ions. Such selectivity is not seen with half salen 1 derived from salicylaldehyde
KEYWORDS
cꢇꢉꢄxꢇꢅꢆnꢆ; ꢁꢋꢅn-ꢃn sꢆnsꢃꢅ;
ꢊꢀꢆꢈꢃdꢃsꢄꢈꢆꢁꢆꢅ
1
and 1-aminopyrene. H NMR analysis reveals that it is a chemodosimetric sensor based on its
2
+
hydrolysis mediated by Hg to release 1-aminopyrene molecules as fluorescent chromophores.
Introduction
applied to the chemodosimetric reaction for the first time
by Kim et al., who found that half-salen-type compound
Mercury is a toxic heavy metal, which causes serious
damage to human beings and the natural environment
+
1
serves as a turn-on fluorescent sensor for Hg2 (4,5).
However, the influence of coexistent metal ions on the
detection has not been reported.
(
1). Therefore, much attention has been paid to the devel-
opment of mercury sensors with high selectivity and
sensitivity (2). Among such entities, fluorescent sensors
are of particular interest, because fluorescent sensing
has advantages of the simplicity of implementation and
fast response over other analytical techniques including
ICP emission analysis. Chemodosimetric sensors for Hg2+
have been developed by using irreversible chemical reac-
Calixarenes (e.g. 2) have been extensively utilized as
molecular scaffolds for sensing devices, because receptor
unit(s) and physicochemical transducer unit(s) can be pre-
organized on a calix skeleton in a three-dimensional fashion
by chemical modifications (6). To date, a number of fluores-
cent sensors with calix skeletons have been developed for
2+
Hg (7,8). Most of them are turn-off sensors using the heavy
2
+
2+
2+
tions mediated by Hg (3). Hydrolysis of a Schiff base was
atom effect of Hg . This causes a problem in detecting Hg
CONTACT Sꢀꢄnꢌꢇ tꢇnꢇkꢇ
sꢀꢄnꢌꢇ.ꢁꢇnꢇkꢇ.d8@ꢁꢃꢀꢃkꢋ.ꢇꢊ.jꢂ; tꢆꢁsꢋꢁꢇꢅꢃ hꢇꢁꢁꢃꢅꢄ
ꢁꢆꢁsꢋꢁꢇꢅꢃ.ꢀꢇꢁꢁꢃꢅꢄ@ꢁꢃꢀꢃkꢋ.ꢇꢊ.jꢂ
Sꢋꢂꢂꢉꢆꢈꢆnꢁꢇꢉ dꢇꢁꢇ fꢃꢅ ꢁꢀꢄs ꢇꢅꢁꢄꢊꢉꢆ ꢊꢇn bꢆ ꢇꢊꢊꢆssꢆd ꢀꢁꢁꢂs://dꢃꢄ.ꢃꢅg/10.1080/10610278.2017.1388510.
©
2017 infꢃꢅꢈꢇ uK lꢄꢈꢄꢁꢆd, ꢁꢅꢇdꢄng ꢇs tꢇꢌꢉꢃꢅ & Fꢅꢇnꢊꢄs Gꢅꢃꢋꢂ

2
S. TANAKA ET AL.
2
+
2+
in the presence of other metal ions, such as Pb and Cd ,
which also exhibit heavy atom effects. In addition, it remains
a challenge to improve the detection sensitivity, as most of
at a low field (10.97 ppm), suggesting the presence of
strong hydrogen bonds between the hydroxy and imino
groups. These observations indicate that the diimine
adopts a cone conformation in the solution. This was sup-
ported by NOESY analysis, which exhibited five cross peaks
between the two aryl signals, one of the two methylene
signals and the two aryl signals, the other methylene signal
and the imino and hydroxy signals.
2+
existing calixarene-based Hg sensors require a large
2+
excess of Hg ions in detection. We have been developing
novel methods to displace the hydroxy groups of calix[4]
arenes with other functional groups (9). We recently pre-
pared 1,3-diphosphonic acid 3 by using one of those meth-
ods and showed that this compound precisely discriminates
the ionic radii of rare-earth metal ions and exhibits high
extraction selectivity toward heavy rare-earth metal ions in
solvent extraction (9b). The performance was superior to
that of its analogue bearing two phosphono groups on two
facing hydroxy oxygens of compound 2 through methylene
linkages. This indicates that in order to achieve high recog-
nition ability toward metal ions, it is favorable to introduce
metal recognition sites onto the calix skeleton in a way that
limits their conformational flexibility. In this study, we have
designed and synthesized diimine 5, in which two facing
hydroxy groups of compound 2 are replaced with pyre-
nyliminomethyl groups, and examined its performance as
The fluorescence spectrum of diimine 5 was meas-
ured in THF/H O (99:1, v/v) in the presence or absence
2
of a metal perchlorate (1 molar equiv) at an excitation
wavelength of 340 nm (Figures 1 and S1); the solvent sys-
tem was chosen in consideration of the reproducibility
of the hydrolysis (vide infra). The diimine itself emitted
almost no fluorescence despite bearing pyrene chromo-
phores (Figure 1). This was attributed to quenching by
strong hydrogen bonds between the imino and hydroxy
groups, as discussed for half salen 1 in the literature (10).
Interestingly, only Hg(ClO ) increased the fluorescence
4
2
intensity dramatically among the metal perchlorates
tested; the ratio of the maximum intensity of the solu-
tion containing diimine 5 and Hg(ClO ) (Imax) to that of
2+
a chemodosimetric turn-on sensor for Hg by fluorescence
spectroscopy.
4
2
the solution containing only diimine 5 (I ) is 271 (Figure
0
2
). The Hg(ClO ) -induced spectrum is in good agreement
4 2
with that of 1-aminopyrene (Figure S2), indicating that this
fluorescence was originated from 1-aminopyrene released
1
from diimine 5. In fact, in H NMR analysis of diimine 5 in
THF-d /D O (99:1), the signals of the diimine completely
8
2
disappeared upon the addition of 10 molar equiv of
Hg(ClO ) and novel signals assigned to dialdehyde 4 and
4
2
1
-aminopyrene appeared (Figure 3). Although metal ions
2
+
other than Hg did not affect much on the fluorescence
intensity of diimine 5, they caused a change in the spec-
tral shape (Figure S1); increasing the amount of the metal
ions (100 molar equiv) made this change clearer (Figure
2
+
S3). This indicates that not only Hg but also other metal
Results and discussion
In a previous paper (9e), we reported a synthetic method
of dialdehyde 4 from tetraol 2 by using Ullmann-type
iodination and formylation of a lithiated intermediate
with N-formylpiperidine as key steps. Diimine 5 could
be readily prepared from dialdehyde 4 by dehydrative
1
condensation with 1-aminopyrene. The H NMR spec-
trum of diimine 5 in CDCl exhibited two singlets (18H
3
each) for the tert-butyl protons, a pair of doublets (4H
each) for the bridging methylene protons, one singlet
(
2H) for the imino protons, and two singlets (4H each)
Figure 1. (cꢃꢉꢃꢋꢅ ꢃnꢉꢄnꢆ) cꢀꢇngꢆ ꢄn ꢁꢀꢆ flꢋꢃꢅꢆsꢊꢆnꢊꢆ sꢂꢆꢊꢁꢅꢋꢈ ꢃf
for the aryl protons of the calix skeleton; the magnetic
equivalences suggest a C -symmetric structure, that is,
cone or 1,3-alternate conformation. In addition, a singlet
signal (2H) assigned to the hydroxy protons appeared
dꢄꢄꢈꢄnꢆ 5 (6 × 10− m) ꢄn thF/h o (99:1, v/v) ꢋꢂꢃn ꢁꢀꢆ ꢇddꢄꢁꢄꢃn
5
2
2
v
ꢃf vꢇꢅꢄꢃꢋs ꢈꢆꢁꢇꢉ ꢄꢃns ꢇs ꢈꢆꢁꢇꢉ ꢂꢆꢅꢊꢀꢉꢃꢅꢇꢁꢆs (1 ꢈꢃꢉꢇꢅ ꢆqꢋꢄv)
(λꢆx = 340 nꢈ).
Nꢃꢁꢆ: eꢇꢊꢀ sꢂꢆꢊꢁꢅꢋꢈ wꢇs ꢅꢆꢊꢃꢅdꢆd 10 ꢈꢄn ꢇfꢁꢆꢅ ꢁꢀꢆ ꢇddꢄꢁꢄꢃn ꢃf ꢇ ꢈꢆꢁꢇꢉ ꢄꢃn.

SUPRAMOLECULAR CHEMISTRY
3
Figure 2. (cꢃꢉꢃꢋꢅ ꢃnꢉꢄnꢆ) Fꢉꢋꢃꢅꢆsꢊꢆnꢊꢆ ꢄnꢁꢆnsꢄꢁꢌ ꢅꢇꢁꢄꢃ Iꢈꢇx/Iꢃ ꢃf ꢇ
Figure 4. (cꢃꢉꢃꢋꢅ ꢃnꢉꢄnꢆ) Fꢉꢋꢃꢅꢆsꢊꢆnꢁ ꢄnꢁꢆnsꢄꢁꢌ ꢃf ꢇ sꢃꢉꢋꢁꢄꢃn ꢃf
−5
−5
sꢃꢉꢋꢁꢄꢃn ꢃf dꢄꢄꢈꢄnꢆ 5 (6 × 10 m) ꢄn thF/h o (99:1, v/v).
dꢄꢄꢈꢄnꢆ 5 (6 × 10 m) ꢄn thF/h o (99:1, v/v) ꢇꢁ 432 nꢈ ꢄn ꢁꢀꢆ
2
2
2
+
Nꢃꢁꢆ: I ꢇnd I dꢆnꢃꢁꢆ ꢁꢀꢆ flꢋꢃꢅꢆsꢊꢆnꢊꢆ ꢄnꢁꢆnsꢄꢁꢌ ꢇꢁ 432 nꢈ ꢄn ꢁꢀꢆ ꢇbsꢆnꢊꢆ
ꢂꢅꢆsꢆnꢊꢆ ꢃf hg ꢇnd ꢇnꢃꢁꢀꢆꢅ ꢈꢆꢁꢇꢉ ꢄꢃn ꢇs ꢈꢆꢁꢇꢉ ꢂꢆꢅꢊꢀꢉꢃꢅꢇꢁꢆs
ꢃ
ꢈꢇx
ꢇnd ꢂꢅꢆsꢆnꢊꢆ ꢃf ꢇ ꢈꢆꢁꢇꢉ ꢄꢃn (1 ꢈꢃꢉꢇꢅ ꢆqꢋꢄv), ꢅꢆsꢂꢆꢊꢁꢄvꢆꢉꢌ.
(1 ꢈꢃꢉꢇꢅ ꢆqꢋꢄv ꢆꢇꢊꢀ).
Nꢃꢁꢆ: Dꢇꢁꢇ ꢇꢅꢆ sꢀꢃwn ꢇs ꢂꢆꢅꢊꢆnꢁꢇgꢆ vꢇꢉꢋꢆs ꢅꢆꢉꢇꢁꢄvꢆ ꢁꢃ ꢁꢀꢆ ꢄnꢁꢆnsꢄꢁꢌ ꢃf ꢇ
sꢃꢉꢋꢁꢄꢃn ꢃf dꢄꢄꢈꢄnꢆ 5 ꢇnd hg(cꢉo ) .
4
2
1
Figure 3. exꢂꢇndꢆd h Nmr sꢂꢆꢊꢁꢅꢇ ꢃf dꢄꢄꢈꢄnꢆ 5 ꢄn thF-d -D o
8
2
(
99:1) bꢆfꢃꢅꢆ (ꢇ) ꢇnd ꢇfꢁꢆꢅ ꢁꢀꢆ ꢇddꢄꢁꢄꢃn ꢃf hg(cꢉo ) (10 ꢈꢃꢉꢇꢅ
4 2
Figure 5. (cꢃꢉꢃꢋꢅ ꢃnꢉꢄnꢆ) Fꢉꢋꢃꢅꢆsꢊꢆnꢁ ꢄnꢁꢆnsꢄꢁꢌ ꢃf ꢇ sꢃꢉꢋꢁꢄꢃn ꢃf
ꢆqꢋꢄv) (b), ꢇs ꢊꢃꢈꢂꢇꢅꢆd ꢁꢃ ꢁꢀꢃsꢆ ꢃf dꢄꢇꢉdꢆꢀꢌdꢆ 4 (ꢊ) ꢇnd ꢇ ꢈꢄxꢁꢋꢅꢆ
ꢃf 1-ꢇꢈꢄnꢃꢂꢌꢅꢆnꢆ ꢇnd hg(cꢉo ) (1:5) (d).
−5
ꢀ
ꢇꢉf sꢇꢉꢆn 1 (12 × 10 m) ꢄn thF/h o (99:1, v/v) ꢇꢁ 432 nꢈ ꢄn ꢁꢀꢆ
2
4
2
2+
ꢂꢅꢆsꢆnꢊꢆ ꢃf hg ꢇnd ꢇnꢃꢁꢀꢆꢅ ꢈꢆꢁꢇꢉ ꢄꢃn ꢇs ꢈꢆꢁꢇꢉ ꢂꢆꢅꢊꢀꢉꢃꢅꢇꢁꢆs
(1 ꢈꢃꢉꢇꢅ ꢆqꢋꢄv ꢆꢇꢊꢀ).
Nꢃꢁꢆ: Dꢇꢁꢇ ꢇꢅꢆ sꢀꢃwn ꢇs ꢂꢆꢅꢊꢆnꢁꢇgꢆ vꢇꢉꢋꢆs ꢅꢆꢉꢇꢁꢄvꢆ ꢁꢃ ꢁꢀꢆ ꢄnꢁꢆnsꢄꢁꢌ ꢃf ꢇ
ions interact with diimine 5. However, their influence on
the fluorescence spectrum of diimine 5 was much smaller
than that of Hg .
sꢃꢉꢋꢁꢄꢃn ꢃf ꢀꢇꢉf sꢇꢉꢆn 1 ꢇnd hg(cꢉo ) .
4
2
2
+
To investigate the influence of coexistent metal ions
on the Hg -mediated hydrolysis of diimine 5, the fluo-
groups of half salen 1, as suggested by the spectral change
of 1 upon the addition of various metal ions (Figure S4b).
2
+
2+
rescence spectrum of diimine 5 was measured in THF/H O
This inhibits the Hg -mediated hydrolysis. Diimine 5 does
not seem to be susceptible to this inhibition, because the
two iminomethyl groups are preorganized in a manner
2
(
99:1, v/v) in the presence of Hg(ClO ) and another metal
4 2
perchlorate (1 molar equiv each). Figure 4 shows Imax for the
solutions containing various coexistent metal perchlorates
2+
suitable for the nitrogen atoms to coordinate to a Hg ion
in a trans fashion. Therefore, it may be concluded that the
as percentage values relative to I for a solution contain-
max
2
+
2+
ing only 5 and Hg(ClO ) . The Hg -mediated hydrolysis
selective detection of Hg in the presence of other metal
4
2
was not much affected by coexistent metal ions; the rel-
ative intensities are more than 88% except Cu(ClO ) . The
ions was achieved by fixing the iminomethyl groups on
the calix skeleton.
4
2
same experiment was performed for half salen 1 (Figure
5
1
). Although the fluorescence spectrum of half salen 1 (i.e.
Conclusion
-aminopyrene) was selectively induced by Hg(ClO ) as in
4
2
the case of diimine 5 (Figure S4a compared to Figure 1),
the fluorescence intensity was seriously affected by most
of the coexistent metal ions tested (Figure 5). Coexistent
metal ions should interact with the imino and/or hydroxy
We have shown here that diimine 5 bearing pyrenylim-
inomethyl moieties serves as a turn-on-type fluorescent
2
+
sensor. It selectively detected Hg in the presence of var-
ious other metal ions. Such selectivity was not seen with

4
S. TANAKA ET AL.
half-salen-type compound 1, suggesting that the selec-
tivity was realized by regulating the dispositions of the
receptor units with the calix skeleton.
Funding
This work was supported in part by Japan Society for the Pro-
motion of Science (JSPS) [grant number KAKENHI 15K05466].
Experimental
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1
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(
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for C H N O ·H O: C, 85.99; H, 7.03; N, 2.57. Found: C,
7
8
74
2
2
2
8
6.06; H, 6.94; N, 2.70.
1
(
(
4) Kim, J.H.; Kim, H.J.; Bae, C.W.; Park, J.W.; Lee, J.H.; Kim, J.S.
Arkivoc 2010, vii, 170–178.
Fluorescence analysis
5) See also: (a) Bhalla, V.; Kumar, M.; Sharma, P.R.; Kaur, T.
Dalton Trans. 2013, 15063–15068. (b) Mukhopadhyay, S.;
Biswas, A.; Pandey, R.; Gupta, R.K.; Pandey, D.S. Tetrahedron
Lett. 2014, 55, 1437–1440. (c) Kumar, A.; Dubey, M.; Pandey,
R.; Gupta, R.K.; Kumar, A.; Kalita, A.C.; Pandey, D.S. Inorg.
Chem. 2014, 53, 4944–4955. (d) Zhang, X.; Zhu, Y.Y. Sens.
Actuators, B Chem. 2014, 202, 609–614. (e) García-Beltrán,
O.; Rodríguez, A.; Trujillo, A.; Cañete, A.; Aguirre, P.; Gallego-
Quintero, S.; Nuñez, M.T.; Aliaga, M.E. Tetrahedron Lett.
Stock solutions of diimine 5 (120 μM) and metal perchlo-
rates (12 mM) in THF/H O (99:1, v/v) were prepared. The
2
stock solutions of diimine 5 (594 μL) and metal perchlo-
rate(s) (6 μL) were mixed, and the resulting solution was
diluted with THF/H O (99:1, v/v) until the volume reached
2
to 1.2 mL. After stirring for a short time, the mixture was
left for 10 min and charged into a 1-cm cell. Fluorescence
spectra were routinely recorded on a Hitachi F-7000 spec-
trometer at an excitation wavelength of 340 nm with an
emission slit-width of 5.0 nm.
2015, 56, 5761–5766.
(
6) For reviews, see: (a) Kim, J.S.; Quang, D.T. Chem. Rev. 2007,
107, 3780–3799. (b) Leray, I.; Valeur, B. Eur. J. Inorg. Chem.
2009, 3525–3535.
(
7) For turn-off type Hg sensor with calixarenes, see: (a)
Talanova, G.G.; Elkarim, N.S.A.; Talanov, V.S.; Bartsch, R.A.
Anal. Chem. 1999, 71, 3106–3109. (b) Métivier, R.; Leray, I.;
Valeur, B. Photochem. Photobiol. Sci. 2004, 3, 374–380. (c)
Kim, J.H.; Hwang, A.-R.; Chang, S.-K. Tetrahedron Lett. 2004,
Disclosure statement
No potential conflict of interest was reported by the authors.
45, 7557–7561. (d) Chen, Q.-Y.; Chen, C.-F. Tetrahedron Lett.

SUPRAMOLECULAR CHEMISTRY
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6
5
(
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(
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