A multi-functional fluorescent sensor for Zn2+ and HSO4? based on a new diarylethene derivative

Article abstract of DOI:10.1016/j.tetlet.2018.07.057

A new photochromic diarylethene derivative with a hydralazine unit was designed and synthesized. It was not only acted as a Zn²⁺ sensor with the fluorescent color change from dark blue to bright orange, but also acted as a fluorescent sensor for HSO₄^? with the fluorescent color change from dark blue to bright blue. Furthermore, the derivative also exhibits multi-addressable switching properties by the stimulations of lights and chemical reagents. Based on these characteristics, two combinational logic circuits were constructed with the emission intensity as the output signals, and the UV/vis lights, chemical species as the input signals.

Full text of DOI:10.1016/j.tetlet.2018.07.057

Accepted Manuscript
−
A multi-functional fluorescent sensor for Zn2+ and HSO4 based on a new
diarylethene derivative
Shiqiang Cui, Shouyu Qiu, Ruimin Lu, Shouzhi Pu
PII:
S0040-4039(18)30950-X
https://doi.org/10.1016/j.tetlet.2018.07.057
TETL 50166
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
1 June 2018
25 July 2018
27 July 2018
Please cite this article as: Cui, S., Qiu, S., Lu, R., Pu, S., A multi-functional fluorescent sensor for Zn2+ and HSO4
−
based on a new diarylethene derivative, Tetrahedron Letters (2018), doi: https://doi.org/10.1016/j.tetlet.
2018.07.057
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−
A multi-functional fluorescent sensor for Zn2+ and HSO4 based on a
new diarylethene derivative
Shiqiang Cui, Shouyu Qiu, Ruimin Lu, Shouzhi Pu*
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University,
Nanchang 330013, PR China
*Corresponding author: E-mail: pushouzhi@tsinghua.org.cn (S. Pu); Tel./Fax: +86-791-83831996.
Abstract: A new photochromic diarylethene derivative with a hydralazine unit was designed and
synthesized. It was not only acted as a Zn2+ sensor with the fluorescent color change from dark blue to
bright orange, but also acted as a fluorescent sensor for HSO4− with the fluorescent color change from
dark blue to bright blue,. Furthermore, the derivative also exhibits multi-addressable switching
properties by the stimulations of lights and chemical reagents. Based on these characteristics, two
combinational logic circuits were constructed with the emission intensity as the output signals, and the
UV/vis lights, chemical species as the input signals.
Keywords: Photochromic diarylethene; Fluorescent sensor; Multi-addressable; Logic circuit.
1

1. Introduction
The development of fluorescent sensors for the recognition of cations or anions has attracted great
research interests due to their important role in biological, clinical and environmental applications.1-7
Zinc is the second most abundant transition metal as well as essential ingredient to preserve life with
2-4 g distributed throughout the human body.8,9 It plays a vital role in many biological processes such
as brain function and pathology, gene transcription, immune function, and mammalian
reproduction,10,11 as well as it is involved in the pathological processes in many diseases including
Alzheimer's disease,12 epilepsy,13 and ischemic stroke.14 Meanwhile, among various anions, the
−
hydrogen sulfate ion (HSO4 ) is of great significance as it is established role in biological and industrial
−
areas.15 The HSO4 eventually dissociates at high pH to generate toxic sulfate radical ion,16 which
causes irritation of the skin, eyes, and even respiratory paralysis.17-19 For these reasons, the effective
and selective detection of Zn2+ and HSO4− ions is of great significance for biochemistry, environmental
−
science and medicine. The development of highly selective fluorescent sensors for Zn2+ and HSO4 is
−
still a great challenge, although some fluorescent sensors for Zn2+ and HSO4 have been reported,
respectively.20-28
In recent years, photochromic compounds have attracted much attention for their potential applications
in data recording and storage,29-31 multi-photon devices,32,33 photo-elctronic devices,34 fluorescent
sensors,35-38 molecular logic gates,39-42 and so forth. Among the reported photochromic compounds for
distinguishing ions, diarylethenes are the most promising materials because of their fast response, high
cyclization/cycloreversion quantum yields, excellent thermal stability, and outstanding fatigue
resistance.43-46 Up to date, many single-identified fluorescent sensors based on diarylethene for cations
have been extensively studied.47-49 However, the multi-identified fluorescent sensors based on
2

diaryelthene have not been reported. Therefore, the multiple functional fluorescent sensors for cations
and anions also have attracted more attention.50-54
Hydralazine was primarily synthesized by Ciba as an anti-hypertensive compound and has long been
known to possess de-methylating activity.55,56 It was first approved by the U.S. Food and Drug
Administration as an anti-hypertensive drug in 1952.57 Today, it has vital place in clinical practice as a
third-line antihypertensive regimen in patients with complicated hypertension, an antihypertensive in
intensive care unit settings, and a second-line therapeutic for chronic heart failure, or because of its
safety profile in pregnancy hypertension.57-62 Recently, two fluorogenic chemosensors for Co2+ based
on hydralazine have been reported.63,64 However, fluorescent sensors for special ions of interest based
on diarylethene with hydralazine unit have not been reported previously. In this work, a new
−
fluorescent sensor for Zn2+ and HSO4 based on a diarylethene containing hydralazine unit was
constructed. The photophysical and photochemical behaviors of the diarylethene derivative (1o) were
investigated systematically. The synthetic route and photochromism of 1o are shown in Scheme 1.
Scheme 1. Synthetic route and photochromism of 1o.
2. Experimental
2.1. General methods
All reagents were purchased from Aldrich and used without further purification. All solvents used were
3

spectral grade and purified by distillation before use. 1H NMR and 13C NMR spectra were collected on
a Bruker AV400 spectrometer by using tetramethylsilane (TMS) as an internal standard and with
DMSO-d6 as the solvent. Infrared spectra (IR) were performed on a PerkinElmer Spectrum
spectrometer. Mass spectra were recorded with an Agilent 1100 ion trap MSD spectrometer. Melting
point was measured on a WRS-1B melting point apparatus. Fluorescence spectra were measured with a
Hitachi F-4600 fluorescence spectrophotometer, and the slit width was 5 nm for both excitation and
emission. Absorption spectra were measured on an Agilent 8453 UV/vis spectrophotometer. The
fluorescence quantum yield was obtained on an Absolute PL Quantum Yield Spectrometer QY
C11347-11. Elemental analysis was carried out with a PE CHN 2400 analyzer. Photoirradiation were
performed on an MUA-165 UV lamp and a MVL-210 visible lamp.
2.2. Synthesis of 1o
The synthetic route of 1o is shown in Scheme 1. Compound 2 was synthesized through Suzuki
coupling reaction according to the previous report,65 after the formyl in compound 2 was protected with
glycol,
compound
3
was
obtained.
Compound
4
was
synthesized
from
3-Bromo-2-methyl-5-phenylthiophene, according to the reported work.66 Subsequently, compound 3
was lithiated in THF at 195 K, and then compound 4 was added. After reacting for 1 h, the reaction
product was hydrolyzed to give diarylethene 5. The experimental procedures and characterized data are
showed in Supporting Information (Experimental procedures details, Fig. S1-S2).
A mixture of 5 (0.28 g, 0.5 mmol) and 1-(pthalazine-4-yl)hydrazine (0.064 g, 0.5 mmol) were dissolved
in 10.0 mL in anhydrous methanol. After stirring and refluxing for 2 h, the mixture was cooled to room
temperature and a green precipitate was obtained. The crude product was purified by recrystallization
with ethanol to give the target diarylethene 1o (0.23 g, 66% yield) as a light green solid. Mp. 426-427
4

K. 1H NMR (400 MHz, DMSO-d6, TMS), δ (ppm): 2.03 (s, 3H), 2.06 (s, 3H), 7.36 (d, 1H, J = 12.0 Hz),
7.44 (d, 2H, J = 16.0 Hz), 7.52 (s, 1H), 7.65 (d, 2H, J = 8.0 Hz), 7.84 (s, 1H), 8.16 (d, 1H, J = 8.0 Hz),
8.21 (d, 2H, J = 8.0 Hz), 8.29 (m, 1H), 8.75 (d, 1H, J = 8.0 Hz), 8.88 (s, 1H), 8.95 (d, 1H, J = 8.0 Hz),
13
8.98 (s, 2H). C NMR (100 MHz, DMSO-d6, TMS), δ (ppm): 13.5, 13.6, 116.7, 119.3, 121.0, 122.0,
123.5, 123.9, 124.4, 124.5, 124.6, 124.8, 127.3, 127.6, 128.7, 129.7, 132.0, 133.3, 135.3, 139.7, 140.7,
141.2, 141.3, 143.9, 147.3, 148.83, 157.2. IR (KBr, υ, cm−1): 3025, 2698, 2488, 1621, 1602, 1472, 1390,
1334, 1272, 1184, 1111, 1092, 1051, 1026, 987, 919, 804, 764, 739, 720, 700, 688, 662; Anal. calcd for
C35H23F6N5S2 (%): C, 60.77; H, 3.35; N, 10.12, found: C, 60.78; H, 3.34; N, 10.11. HRMS-ESI, m/z =
692.1414 [M+H+]+ (calcd, 692.1377) (Fig. S3-S6).
3. Results and discussion
3.1 Photochromic and fluorescent properties of 1o
The UV-vis absorption spectral and color changes of 1o induced by photoirradiation were measured in
THF (2.0 × 10−5 mol L−1) at room temperature. As shown in Fig. 1A, 1o exhibited a maximum
absorption band centered at 403 nm (ε = 4.02 × 104 mol−1 L cm−1), which was resulted from π → π*
transition.67 Upon irradiation with 297 nm light, the colorless solution turned into cyan and a new
visible absorption band centered at 607 nm (ε = 1.76 × 104 L mol−1 cm−1) appeared and increased due
to the formation of the closed-ring isomer 1c.68 Simultaneously, the absorption band centered at 403 nm
decreased evidently. Reversely, upon irradiation with visible light (λ > 500 nm), the absorption
spectrum was recovered to that of 1o, accompanied by the cyan solution was bleached completely. In
the photostationary state (PPS), a clearly isosbestic point was observed at 440 nm, indicating that this is
a unimolecular process.69 The quantum yields of cyclization and cycloreversion were determined to be
0.24 and 0.014, respectively, using 1,2-bis(2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene as
5

reference.70 The fatigue resistance of 1o was tested in THF through alternating irradiation with UV and
visible lights at room temperature. The results showed that the coloration/decoloration cycles of 1o
could be repeated for 20 times with 6.2% degradation (Fig. S7).
60
1.0
0 s
5 s
UV
Vis
UV
50
40
30
20
10
0
Vis
10 s
20 s
40 s
60 s
80 s
0.8
0.6
0.4
0.2
0.0
Vis
UV
450
500
550
600
650
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
(A)
(B)
Fig. 1. The absorption (A) and fluorescence (B) spectra changes of 1o (2.0 × 10-5 mol L-1) upon
alternating irradiation with UV/vis lights in THF, when excited at 400 nm.
The fluorescent properties of 1o were also examined. As shown in Fig. 1B, the emission peak of 1o was
observed at 491 nm with 400 nm excitation. The absolute fluorescence quantum yield of 1o was
determined to be 0.002. Upon irradiation with 297 nm light, the emission intensity of 1o decreased
remarkably, due to the non-fluorescence isomer 1c was formed. When the PPS was reached, the
emission of 1o was decreased by ca. 89.2%, indicating that the diarylethene exhibited high
fluorescence modulation efficiency. The residual fluorescence in the PSS may be attributed to the
incomplete cyclization reaction and the existence of the open-ring isomer with parallel conformation.71
Inversely, the open-ring isomer 1o could be regenerated and the original emission spectrum could be
recovered upon irradiation with visible light (λ > 500 nm).
3.2 Selectivity of 1o towards Zn2+
In order to study the selectivity of 1o towards Zn2+, the interaction between 1o and various metal ions
6

including Zn2+, Cd2+, Al3+, Cr3+, Fe3+, Ba2+, Mn2+, Hg2+, Pb2+, Ca2+, Sr2+, Mg2+, Ni2+, Co2+, Cu2+, Fe2+,
and K+ were investigated in THF solution. As shown in Fig. 2, when 35.0 equiv. Zn2+ were added, the
fluorescence of 1o at 594 nm was enhanced greatly, accompanied by the fluorescent color changed
from blue to bright orange. The enhancement of emission intensity was attributed to the formation of
1o-Zn2+ (1o′) complex. When 1o was coordinated with Zn2+, due to the stable complexation between
1o and Zn2+ prohibited the PET process, a large CHEF effect was observed. Furthermore, the stable
chelation of 1o and Zn2+ inhibited the C═N isomerization and rigidification of fluorophore
structure.63,64 There were no changes in fluorescence of 1o, when the same amounts of other ions were
added. These results indicated that the diarylethene 1o could act as a fluorescent sensor for Zn2+ with
prominent selectivity.
10
500
Zn2+
8
400
6
300
4
Blank and other ions
200
2
100
Cd2+
0
0
+
2+
2+
3+
3+
3+
2+
2+
2+
2+
2+
2+
2+
2+
2+
2+
2+
e
500
600
700
800
n
K
Al
Ni
Sr
Cr
Fe
Fe
Co Cu
Zn
-2
Ba
Pb Ca
Hg
Cd
Mn
Mg
No
Wavelength/nm
(A)
(B)
(C)
Fig. 2. Changes in the fluorescence of 1o induced by the addition of various metal ions (35.0 equiv.) in
THF (2.0 × 10-5 mol L-1, λex = 400 nm): (A) fluorescence spectral changes; (B) emission intensity
changes; (C) photos of fluorescence.
7

Subsequently, a fluorometric titration experiment was carried out in THF (2.0  10-5 mol L-1) at room
temperature to investigate the fluorescence responsive of 1o to Zn2+. As shown in Fig. 3A, the emission
intensity at 594 nm increased when Zn2+ was increased from 0 to 35.0 equiv., followed by a plateau
with further titration. Compared to 1o, the emission peak has a redshift of 103 nm, and the emission
intensity of 1o′ was enhanced by 9.5 fold at the plateau. A notable fluorescent color was changed from
dark blue to bright orange. The absolute fluorescence quantum yield of 1o′ was determined to be 0.023.
To examine the coordination process of 1o with Zn2+ was reversible or not, the chelating agent EDTA
was added to the solution of 1o′. The fluorescence spectrum of 1o′ recovered immediately to that of 1o,
when 70.0 equiv. EDTA were added. The result suggested that the complexation-decomplexation
reaction between 1o and Zn2+ was reversible. Upon irradiation with 297 nm light, the emission intensity
of 1o′ decreased and the fluorescent color changed from bright orange to light yellow, due to the
closed-ring isomer 1c-Zn2+ (1c′) complex was formed. In the PSS, the emission intensity was quenched
by ca. 66.8%, indicating that 1c′ also exhibited strong fluorescence modulation efficiency (Fig. 3B).
The emission intensity of 1o′ could be recovered upon irradiation with visible light (λ > 500 nm).
Furthermore, the fluorescence responsive of 1c to Zn2+ was also investigated. As shown in Fig. S8A,
Compared to 1c, the emission intensity increased about 16.5 fold when Zn2+ was increased from 0 to
35.0 equivalents. The absolute fluorescence quantum yield of 1c′ was determined to be 0.003.
8

500
400
300
200
100
0
500
400
300
200
100
0
Zn2+
500
400
300
200
100
0
EDTA
Vis
UV
35 equiv.
Zn2+
0
10
20
30
40
50
60
Equiv Zn2+
0
450
500
550
600
650
700
750
450
500
550
600
650
700
750
Wavelength (nm)
Wavelength (nm)
(A)
(B)
Fig. 3. (A) The fluorescence changes of 1o (2.0 × 10-5 mol L-1, λex = 400 nm) induced by Zn2+; (B) the
fluorescence changes of 1o′ upon irradiation of UV/vis lights.
To make sure the binding mode between 1o and Zn2+, a Job’s plots analysis was calculated by using the
emission intensity at 594 nm as a function of the molar fraction of 1o. As shown in Fig. 4A, the
intensity approached the maxima when the molar fraction of [1o] / ([Zn2+] + [1o]) was about 0.5,
indicating that 1o was bound to Zn2+ with a binding stoichiometry of 1 : 1. The HRMS peaks at
754.0507 m/z assigned to [1o-H++Zn2+]+ (calcd. 754.0501) was observed (Fig. S9), which provided
another evidence for the formation of a 1 : 1 complex between 1o and Zn2+. The relationship between
F0 / (F-F0) and [Zn2+]-1 were obtained from the fluorescence titration profiles for the plots measured at
594 nm and the association constants (Ka) of 1o and Zn2+ could be calculated with the
Benesi-Hildebrand equation.72 Based on the 1 : 1 binding mode and the fluorescence titration data, the
Ka was determined to be 6.0 × 103 L mol-1 (Fig. S10A). According to the reported method,73 the
detection limit was calculated to be 9.47 × 10-6 mol L-1 for Zn2+ (Fig. S11A). Based on these facts, the
proposed binding mode between 1o and Zn2+ was shown in Scheme 2.
9

40
30
20
10
0
180
150
120
90
60
30
0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
[1o]/[HSO4-]+[1o]
[1o]/[Zn2+]+[1o]
(A)
(B)
Fig. 4. Job’s plot showing the 1 : 1 complex of 1o with Zn2+ (A), and the 1 : 1 complex of 1o with
−
HSO4 (B).
−
Scheme 2. Structure fluorescence color changes of 1o induced by Zn2+ and HSO4 .
−
3.3 Fluorescent response of 1o toward HSO4
−
−
3−
The fluorescence selectivity of 1o toward various anions (HSO4 , SO42−, SO32−, H2PO4 , HPO42−, PO4
,
−
−
−
HCO3 , CO32−, NO3 , NO2 , SCN−, CN−, CH3COO−, F−, Cl−, Br−, and I−) was measured in THF. As
−
shown in Fig. 5, only HSO4 caused notable emission intensity and fluorescent color changes. When
−
HSO4 was added, the emission intensity at 491 nm was enhanced by 46.7 fold, along with the
fluorescent color change from dark blue to bright blue. There were no changes in the emission intensity
upon addition of other anions. The results suggested that 1o could also be used as a fluorescent sensor
−
for HSO4 in THF with high selectivity.
10

50
40
30
20
10
0
2500
2000
1500
1000
500
-
HSO4
0
-
-
-
-
-
-
-
-I
-
-
2-
2-
2-
3-
2-
2-
2-
e
N
F
n
4
3
4
O
4
3
4
O
PO
4
3
3
2
Cl
450
500
550
600
650
700
750
Br
o
C
CO NO NO
S
HCO
CN
OO
S
PO
2
P
H
N
SO SO
C
H
H
3
CH
Wavelength (nm)
(A)
(B)
(C)
Fig. 5. Changes in the fluorescence of 1o induced by the addition of various anions (50.0 equiv.) in
THF (2.0 × 10-5 mol L-1, λex = 400 nm): (A) fluorescence spectral changes; (B) emission intensity
changes; (C) photos of fluorescence.
The fluorometric titration experiment with HSO4− was also carried out in THF at room temperature. As
shown in Fig. 6A, when HSO4− was increased from 0 to 50.0 equivalents, the emission intensity of 1o
−
at 491 nm gradually increased due to the formation of 1o-HSO4 (1o′′), followed by a plateau with
further titration. Compared with 1o, the emission intensity of 1o′′ was enhanced 46.7 fold at the plateau,
accompanied by a notable fluorescent color changed from dark blue to bright blue. At the plateau, the
absolute fluorescence quantum yield of 1o′′ was determined to be 0.032. Upon irradiation with 297 nm
light, the emission intensity of 1o′′ was quenched dramatically, accompanied by the fluorescent color
−
change from bright blue to dark blue, due to the formation of the non-fluorescence isomer 1c-HSO4
(1c′′). At the PSS, the emission intensity of 1o′′ was quenched by ca. 91% (Fig. 6B), indicating that
11

1o′′ exhibited relatively strong fluorescence modulation efficiency in THF. Reversely, upon irradiation
with visible light (λ > 500 nm), the open-ring isomer 1o′′ was regenerated and the original emission
−
intensity was recovered. In addition, the fluorometric titration of 1c with HSO4 was also performed
−
under the same conditions (Fig. S8B). The emission intensity increased about 15.4 fold, when HSO4
was increased from 0 to 50.0 equivalents, and the emission intensity remained constant with further
titration. The absolute fluorescence quantum yield of 1c′′ was determined to be 0.009.
2500
2000
1500
1000
500
2500
2000
1500
1000
500
2500
2000
1500
1000
500
50.0 equiv.
UV
Vis
-
HSO4
0
0
0
20
40
60
80
Equiv HSO4-
0
0
450
500
550
600
650
700
450
500
550
600
650
700
Wavelength (nm)
Wavelength (nm)
(A)
(B)
−
Fig. 6. The fluorescence change of 1o (2.0 × 10-5 mol L-1, λex = 400 nm) induced by HSO4 (A), and the
fluorescence change of 1o′′ upon irradiation of UV/vis light (B).
−
The Job's plot analysis was also performed to study the binding mode between 1o and HSO4 . As
−
shown in Fig. 4B, when the molar fraction of [1o] / ([HSO4 ] + [1o]) was about 0.5, the maximum
−
value achieved, indicating that the stoichiometry between 1o with HSO4 was 1 : 1. From the
−
Benesi–Hildebrande equation, the binding constant of 1o with HSO4 was calculated to be 2.65 × 102 L
mol-1 based on the 1 : 1 binding mode (Fig. S10B). Additionally, the fluorescence titration profile
−
demonstrates that 1o has a detection limit of 1.3 × 10−5 mol L−1 for HSO4 (Fig. S11B). According to
−
the previous report,74,75 the proposed binding mode between 1o and HSO4 is via intermolecular
hydrogen-bonding and is shown in Scheme 2.
12

−
Scheme 3 Structure, color, and fluorescence changes of 1o induced by Zn2+/EDTA, HSO4 , and UV/vis
lights.
3.4 Application in logic circuits
The emission intensity of 1o could be modulated by the stimuli of UV/vis lights and chemical. The
multi-addressable fluorescence switching behaviors of 1o are shown in Scheme 3. On the basis of the
facts mentioned above, two molecular logic circuits were constructed, one has four inputs (In1: 297 nm
light, In2: λ > 500 nm visible light, In3: Zn2+, and In4: EDTA) and one output (Output 1: the change in
the emission intensity at 594 nm), the other has three inputs (In1: 297 nm light, In2: λ > 500 nm visible
−
light, and In5: HSO4 ) and one output (Output 2: the change in the emission intensity at 491 nm). As
shown in Fig. 7, the emission intensity of 1o at 491 nm was regarded as an initial value. When the
emission intensity at 594 nm was 9.5 fold lager than the initial value, the output could be regarded as
‘on’ state with a Boolean value of ‘1’, otherwise, it was regarded as ‘off’ state with a Boolean value of
‘0’. Under the stimuli of the four inputs, the diarylethene showed an on-off-on colorimetric switching
behavior. Subsequently, there would read a string of four inputs and write one output. For example,
13

when the string is ‘0, 0, 1, and 0’, the corresponding input signals of In1, In2, In3, and In4 are ‘off, off,
on, and off’. Under these conditions, 1o was converted to 1o′ with the addition of Zn2+, and its
emission intensity at 594 nm is increased significantly. As a result, the output signal Output 1 was ‘on’,
and the Boolean value was ‘1’. Similarly, different combinational strings could result different outputs.
All possible logic strings concluded the logic circuit are concluded and shown in Table 1.
Table 1 Truth table for all possible strings of four binary-input data and the corresponding output digit.
Input
In3 (Zn2+)
Output 1
λem = 594 nm
In1 (UV light)
In2 (Vis light)
In4 (EDTA)
0
1
0
0
0
1
1
1
0
0
0
1
1
1
0
1
0
0
1
0
0
1
0
0
1
1
0
1
1
0
1
1
0
0
0
1
0
0
1
0
1
0
1
1
0
1
1
1
0
0
0
0
1
0
0
1
0
1
1
0
1
1
1
1
0
0
0
1
0
0
0
0
1
0
0
1
0
0
0
0
Fig. 7. The combinational logic circuit equivalent to the truth table given in Table1: In1 (297 nm light),
In2 (λ > 500 nm light), In3 (Zn2+), In4 (EDTA) and Output 1 (fluorescence at 594 nm).
14

In another combinational logic circuit (Fig. 8), when the emission intensity at 491 nm was 46.7 fold
larger than the initial value, the output signal Output 2 was regarded as ‘on’ state. Under the stimuli of
the three inputs, 1o also showed “on-off-on” fluorescence switching behaviors. Consequently, 1o could
read a string of three inputs and write one output. All possible logic strings of the combinational logic
circuit are concluded and listed in Table 2.
Table 2. Truth table for all possible strings of three binary-input data and the corresponding output digit.
Input
Output 2
-
λem = 491 nm
In1 (UV)
In2 (Vis)
In5 (HSO4 )
0
0
1
0
1
0
1
1
0
0
0
1
0
1
1
1
0
1
0
0
1
1
0
1
0
1
0
0
0
1
0
1
Fig. 8. The combinational logic circuit equivalent to the truth table given in Table2: In1 (297 nm light),
−
In2 (λ > 500 nm light), In5 (HSO4 ) and Output 2 (fluorescence at 491 nm).
4. Conclusion
In summary, a novel diarylethene derivative with a hydralazine unit was designed and synthesized. It
−
exhibited high selectivity toward Zn2+ and HSO4 , respectively. The fluorescent spectral studies
revealed that Zn2+ could induce the emission peak for 103 nm redshift, and the emission intensity
enhanced 9.5 fold, accompanied by the fluorescent color change from dark blue to bright orange. The
15

−
added HSO4 could induce the emission intensity enhanced 46.7 fold, accompanied by the fluorescent
color changed from dark blue to bright blue. Furthermore, based on the multi-addressable fluorescence
switching characteristics, two logic circuits were constructed with the emission intensity as output
−
signals and the UV/vis lights, Zn2+/EDTA, or HSO4 as input signals. This work will be helpful for a
new approach to design fluorescent sensors for the detection of multiple ions, and to construct
multi-state diarylethene for logic circuits.
Acknowledgments
The authors are grateful for the financial support from the Project of the Science Funds of the
Education Office of Jiangxi (GJJ160773), the “5511” science and technology innovation talent project
of Jiangxi (2016BCB18015), the key project of Natural Science Foundation of Jiangxi Province
(20171ACB20025), the Young Talents Project of Jiangxi Science and Technology Normal University
(2015QNBJRC004), and the PhD Start-up Fund of Jiangxi Science and Technology Normal University.
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Graphical Abstract
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A multi-functional fluorescent sensor for Zn2+ and HSO4 based on a
new diarylethene derivative
Shiqiang Cui, Shouyu Qiu, Ruimin Lu, Shouzhi Pu*
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science and Technology Normal University,
Nanchang 330013, China
*Corresponding author: E-mail: pushouzhi@tsinghua.org.cn (S. Pu); Tel./Fax: +86-791-83831996.
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Highlights
> This paper reports a new diarylethene with a hydralazine unit that was designed and synthesized
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for the first time. > The diarylethene could act as a fluorescent sensor for Zn2+ and HSO4 . > The
diarylethene also could be used to construct molecular logic circuits.
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