A new colorimetric and fluorescent bifunctional probe for Cu2+ and F- ions based on perylene bisimide derivatives

Article abstract of DOI:10.1016/j.tetlet.2014.03.137

A perylene bisimide derivative (PBI) based colorimetric and fluorescent bifunctional probe PAM-PBI was designed and synthesized. It was highly selective and sensitive for distinguishing both Cu²⁺ and F^- from other ions through a conspicuous change of UV-vis and fluorescence spectra. The recognition of Cu²⁺ by PAM-PBI showed an obvious color change from rose red to purple in aqueous solution, while the sensing of F^- gave a marked color change from rose red to light green in THF.

Full text of DOI:10.1016/j.tetlet.2014.03.137

Tetrahedron Letters 55 (2014) 3218–3222
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
A new colorimetric and fluorescent bifunctional probe for Cu2
and F ions based on perylene bisimide derivatives
+
ꢀ
⇑
Yefeng Wang, Liang Zhang, Guanjun Zhang, Yue Wu, Shengying Wu, Jianjun Yu, Limin Wang
Key Laboratory for Advanced Material, and Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A perylene bisimide derivative (PBI) based colorimetric and fluorescent bifunctional probe PAM-PBI was
Received 22 November 2013
Revised 21 March 2014
Accepted 31 March 2014
Available online 5 April 2014
2+
ꢀ
designed and synthesized. It was highly selective and sensitive for distinguishing both Cu and F from
2+
other ions through a conspicuous change of UV–vis and fluorescence spectra. The recognition of Cu by
PAM-PBI showed an obvious color change from rose red to purple in aqueous solution, while the sensing
ꢀ
of F gave a marked color change from rose red to light green in THF.
Ó 2014 Elsevier Ltd. All rights reserved.
Keywords:
Perylene bisimide derivatives
Colorimetric
Fluorescent
Bifunctional probe
Fluorescent chemosensors are widely used as powerful tools of
recognizing and sensing cations and anions owing to their high
sensitivity, selectivity, versatility, and relatively simplicity. In par-
Consequently, considerable effort has been devoted to the design
of fluorescent sensors for Cu and F .
2
+
ꢀ 16–25
1
Perylene dianhydride (PTCDA) and its derivatives (PBIs), as a
representative of strongly fluorescent high performance pigments,
have excellent chemical, thermal, photo, and weather stability.26 In
addition to their use as important industrial pigments, many PBIs
also exhibit near-unity fluorescence quantum yields, high photo-
chemical stability, and strong electron-accepting character. In this
case, significant progress has been made to use PBIs-containing
materials in organic field effect transistors (OFETs), fluorescent
solar, collectors, electrophotographic devices, dye lasers, organic
ticular, the design of sensors capable of recognizing and sensing
both cations and anions, which are also called bifunctional probes,
is one of the most challenging fields because of their significance in
biological, chemical, and environmental processes.2
–6
2
+
Copper, as the third most abundant element (after Fe and
Zn2+) among essential heavy metal ions present in the human
body, plays a critical role in many fundamental physiological pro-
7
cesses. Copper kills a variety of potentially harmful pathogens and
2
7–29
hence has antimicrobial effect against MRSA, Escherichia coli, and
photovoltaic cells (OPVs), and optical power limiters.
Thanks
8
–10
2+
other pathogens.
However, on excessive intake, Cu causes
to their excellent optical and electrical properties, they can be used
3
0–37
injurious effects such as neurodegenerative diseases (e.g., Alzhei-
mer’s and Wilson’s diseases) due to its participation in the produc-
tion of reactive oxygen species.11
as good platforms in the design of fluorescent sensors.
How-
ever, rare even none bifunctional chemosensors based on PBIs
were reported.
Additionally, fluoride has drawn wide attention thanks to its
beneficial effects in preventing dental caries and in the treatment
Herein, we designed a new colorimetric and fluorescent bifunc-
tional probe PAM-PBI for detection of both Cu and F based on
2
+
ꢀ
1
2,13
of osteoporosis.
Moreover, fluoride ions are associated with
PBIs. It showed drastic fluorescence quench and obvious color
2
+
anesthetics, hypnotics, psychiatric drugs, nerve gases, in the anal-
ysis of drinking water and in the refinement of uranium used in
nuclear weapon manufacture. Nevertheless, when administrated
in high dose, it is dangerous and can lead to dental or skeletal
change toward its binding of Cu
in buffered THF/MOPS
ꢀ
(v/v = 4:1) solution and its interaction with F in THF with high
selectivity and sensitivity.
PAM-PBI was obtained from PTCDA via imidization, nitration,
reduction, and acetylation steps, as shown in Scheme 1 (Supple-
mentary data).
1
4,15
fluorosis.
Thus, the diversity of their functions, both beneficial and other-
wise, makes the detection of copper and fluoride ions important.
Both UV–vis absorption and fluorescent emission studies
2+
revealed that PAM-PBI showed selectivity toward Cu in THF/
MOPS (v/v = 4:1, pH = 7.2) solution. As shown in Figure 1a, in the
⇑
Corresponding author. Tel./fax: +86 21 64253881.
E-mail address: wanglimin@ecust.edu.cn (L. Wang).
2
+
absence of Cu
, the maximum absorption wavelength of
http://dx.doi.org/10.1016/j.tetlet.2014.03.137
040-4039/Ó 2014 Elsevier Ltd. All rights reserved.
0

Y. Wang et al. / Tetrahedron Letters 55 (2014) 3218–3222
3219
O
O
O
O
O
O
O
N
O
O
O
O
N
O
O
2
-ethylhexylamine
CAN,HNO3
CH Cl
NO2
DMF
2
2
O
N
N
PTCDA
1
2
O
HO
N
SOCl2
O
O
N
O
O
O
O
N
N
O
O
O
Cl
O
N
Zn,CH COOH
3
NH2
N
H
N
THF
triethylamine,THF
N
3
PAM-PBI
Scheme 1. The synthetic route of PAM-PBI.
(
a) 0.5
PAM-PBI,PAM-PBI+other metal ions
(b)
PAM-PBI,PAM-PBI+other metal ions
6
4
2
00
00
00
0.4
0.3
0.2
0.1
0.0
2+
PAM-PBI+Cu
2+
PAM-PBI+Cu
0
5
00
600
700
800
4
00
500
600
700
Wavelength(nm)
Wavelength(nm)
M) before and after adding 10 equiv of various cations (other metal ions: Ba2+, Cd2+, Ag , Pb2+, Mg2+, Mn2+
+
,
Figure 1. UV–vis (a) and fluorescence (b) spectra of PAM-PBI (10
Cr , Zn , Co , Ni , Fe , Ca , Hg ) in buffered THF/MOPS (v/v = 4:1) solution at pH 7.2.
l
3+
2+
2+
2+
2+
2+
2+
PAM-PBI was at 531 nm (
e
= 41,900). Subsequently, 10 equiv of
obvious change of the absorption could be observed, while the
addition of Cu to PAM-PBI resulted in a slight bathochromic shift
2+
2+
+
2+
2+
2+
3+
2+
2+
different ions, such as Ba , Cd , Ag , Pb , Mg , Mn , Cr , Zn
,
2
+
2+
2+
2+
2+
Co , Ni , Fe , Ca , and Hg was added to measure the selectivity
and synchronous decrease in the absorption band at 531 nm.
2
+
2+
of PAM-PBI to Cu . Upon addition of different metal ions, no
Meanwhile, compared to other metal ions, only Cu generated

3
220
Y. Wang et al. / Tetrahedron Letters 55 (2014) 3218–3222
2
+
Cu /equiv.
0
2+
(a)
(b) 600
600
450
Cu /equiv.
0
0.4
0.3
0.2
0.1
0.0
0
0
0
0
0
0
0
.05
.10
.15
.20
.25
.30
.35
0
0
0
.05
.10
.15
300
450
150
0
0.20
0
0
0
.25
.30
.35
0.0
0.2
0.4
0.6
0.8
1.0
2
+
Cu /equiv.
0.40
300
0.40
0
0
0
0.60
0
.45
.50
.55
0
0
0
0
0
1
.45
.50
.55
.60
.65
.00
150
0
.65
.00
1
400
500
600
700
500
600
700
800
Wavelength(nm)
Wavelength(nm)
Figure 2. UV–vis (a) and fluorescence (b) spectra of PAM-PBI (10 l
M) on addition of Cu2+ (0–1 equiv) in buffered THF/MOPS (v/v = 4:1) solution at pH 7.2. Inset: fluorescence
2
+
intensity at 596 nm of PAM-PBI as a function of Cu equivalent.
an approximately 27-fold fluorescence quench at 596 nm (Fig. 3b)
quantum yield, = 0.693, = 0.026). No significant fluores-
cence change was observed in the presence of other metal ions
excitation at 457 nm, the fluorescence intensity at 596 nm
quenched linearly in the range of 0–0.5 equiv (Fig. S1). The linear
(
U
0
U
1
equation
was
found
to
be
y = 524.08172 ꢀ 98.67246x
(
Fig. 1b). These results demonstrated the high selectivity of PAM-
(R = 0.99186), where y was the intensity at 596 nm measured at
a given Cu concentration and x represented the concentration
2
+
2+
PBI toward Cu
.
The absorption and fluorescence titration of Cu2 was carried
+
(lM) of Cu added. According to IUPAC, the detection limit was
2+
out using a solution of 10
lM PAM-PBI in THF/MOPS (v/v = 4:1).
As illustrated in Figure 2, upon addition of increased amounts of
2
+
Cu , the absorbance of PAM-PBI at 531 nm decreased gradually
and increased at a new band (>531 nm) without an obvious peak.
The rose red solution of free PAM-PBI turned purple and exhibited
two isosbestic points at 457 nm and 559 nm (Fig. 3a). Upon the
600
450
300
150
0
(a)
(b)
2
+
2+
PAM-PBI CU
PAM-PBI
CU
1
2
3
4
5
6
7
8
9
10 11 12 13 14
lM) in the presence of other
Figure 4. Fluorescence intensities of PAM-PBI (10
related metal ions and Cu2 mixtures in buffered THF/MOPS (v/v = 4:1) solution at
pH 7.2. The black bars represent the emission intensities of PAM-PBI or PAM-PBI in
the presence of different metal ions, the red bars represent the emission intensities
+
2
+
of PAM-PBI in the presence of different metal ions (100 lM) and Cu (10 lM). 1:
2+
2+
2+
3+
2+
2+ 2+
2+
Figure 3. Color (a, left) and fluorescence (b, right) change of probe PAM-PBI upon
no metal ion; 2: Pb ; 3: Mg ; 4: Mn ; 5: Cr ; 6: Zn ; 7: Co ; 8: Fe ; 9: Cd ; 10:
addition of Cu2 (1 equiv).
+
Ba ; 11: Ni ; 12: Zn ; 13: Ca2+; 14: Hg2+
2+
2+
2+
.
O
N
O
O
O
N
N
O
O
O
O
N
N
O
O
N
O
N
H
Cu2+
Cu2+
N
H
N
N
H
N
O
O
N
O
O
Scheme 2. Graphic of proposed mechanism of sensing Cu2+
.

Y. Wang et al. / Tetrahedron Letters 55 (2014) 3218–3222
3221
-
F /equiv.
(
b)
(a)
(
a)
F-
0
1
2
3
4
5
6
7
8
9
PAM-PBI
F-
PAM-PBI
0.6
0.4
0.2
0.0
1
0
11
12
13
14
15
Figure 5. Color (a, left) and fluorescence (b, right) change of probe PAM-PBI upon
ꢀ
400
500
600
700
800
addition of F (15 equiv).
Wavelength(nm)
-
F /equiv.
(b)
1000
0
1
2
3
4
5
1000
750
500
250
0
800
600
400
200
0
7
50
00
6
0
2
4
6
8
10
12
14
16
-
7
8
9
F /equiv.
5
1
1
1
1
1
1
0
1
2
3
4
5
250
-
-
-
-
-
-
-
0
PAM-PBI Cl
Br
I
H PO4 HSO4 AcO
F
2
500
600
700
800
Wavelength(nm)
Figure 6. Selectivity of PAM-PBI (10
15 equiv) in THF.
lM) upon addition of different anions
(
Figure 7. UV–vis (a) and fluorescence (b) spectra of PAM-PBI (10
l
M) on addition
ꢀ
of F (0–15 equiv) in THF. Inset: fluorescence intensity at 596 nm of PAM-PBI as a
ꢀ
function of F equivalent.
determined from three times the standard deviation of the blank
signal (3s) as 0.17 mM. Every measure mentioned above was fin-
ished within 1 min, which meant the sensor is real-time. These
results proved that PAM-PBI could serve as a sensitive fluorescent
To further examine the effective application of PAM-PBI, the
competition experiment was carried out. As shown in Figure 4, in
2+
the presence of relevant analytes, the addition of Cu
still
2
+
2+
probe for Cu . According to Job’s plot (Fig. S2), PAM-PBI and Cu
quenched the fluorescence of PAM-PBI, which indicated that the
formed a 2:1 stoichiometry complex, as shown in Scheme 2. The
binding mode of PAM-PBI and Cu2 was confirmed by MALDI-
TOF-MS (Supplementary data) in which a maximum peak is found
2+
detection of Cu was not interfered, thus PAM-PBI displayed a
+
2+
high selectivity for Cu even under competition.
In addition to the cation binding properties, we also investigated
at m/z 1531.6 [(2PAM-PBI + Cu2 + H ) ].
+
ꢀ +
the sensing properties of PAM-PBI for anions. 15 equiv of different
The quenching phenomenon could be explained by two factors.
ꢀ
ꢀ
ꢀ
ꢀ
2ꢀ
ꢀ
ꢀ
anions (F , Cl , Br , I , S , H PO , AcO ) was added into 10 lM
2 4
2
+
Firstly, Cu bound to N atoms of the amide and pyridine moiety
PAM-PBI in THF. UV–vis spectra (Fig. S3) showed that the absorp-
from two equivalent of PAM-PBI, which resulted in the energy
0
tion of PAM-PBI at 531 nm (
e
= 53,700) decreased prominently
2+
transfer from PAM-PBI to Cu . The second factor may be attrib-
and a new absorption band at 692 nm appeared upon the addition
uted to the paramagnetic property of Cu2
+ 38
.
ꢀ
of F , and the fluorescence intensity at 596 nm experienced a
O
O
N
N
O
O
O
O
N
N
O
O
O
F-
N
H
N
N
N
H
F
O
ꢀ
Scheme 3. Graphic of proposed mechanism of sensing F .

3
222
Y. Wang et al. / Tetrahedron Letters 55 (2014) 3218–3222
0
drastic quench (Fig. 5b) (quantum yield,
result, the solution color changed from rose red to light green
Fig. 5a). However, both absorbance and fluorescence intensity of
U
0
ꢁ 1,
U
2
= 0.093). As a
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(
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ꢀ
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Supplementary data
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Supplementary data (Supplementary material contains detailed
1
synthesis process, H NMR, HRMS spectra of PAM-PBI and
Figs. S1–S6.) associated with this article can be found, in the online
version, at http://dx.doi.org/10.1016/j.tetlet.2014.03.137.