Two benzoyl coumarin amide fluorescence chemosensors for cyanide anions

Article abstract of DOI:10.1016/j.saa.2017.04.008

Two new benzoyl coumarin amide derivatives with ortho hydroxyl benzoyl as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions in acetonitrile have also been examined. The influence of electron donating diethylamino group in coumarin ring and hydroxyl in benzoyl group on recognition properties was explored. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectral change and high sensitivity. The import of diethylamine group increases smartly the absorption ability and fluorescence intensity of the compound, which allows the recognition for cyanide anions can be observed by naked eyes. The in situ hydrogen nuclear magnetic resonance spectra combining photophysical properties change and job's plot data confirm that Michael addition between the chemosensors and cyanide anions occurs. Molecular conjugation is interrupted, which leads to fluorescence quenching. At the same time, there is a certain extent hydrogen bond reaction between cyanide and hydroxyl group in the compounds, which is beneficial to the recognition.

Full text of DOI:10.1016/j.saa.2017.04.008

Accepted Manuscript
Two benzoyl coumarin amide fluorescence chemosensors for
cyanide anions
Zian Wang, Qianqian Wu, Jiale Li, Shuang Qiu, Duxia Cao,
Yongxiao Xu, Zhiqiang Liu, Xueying Yu, Yatong Sun
PII:
S1386-1425(17)30275-5
doi: 10.1016/j.saa.2017.04.008
SAA 15061
DOI:
Reference:
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
To appear in:
Received date:
Revised date:
Accepted date:
24 January 2017
29 March 2017
9 April 2017
Please cite this article as: Zian Wang, Qianqian Wu, Jiale Li, Shuang Qiu, Duxia Cao,
Yongxiao Xu, Zhiqiang Liu, Xueying Yu, Yatong Sun , Two benzoyl coumarin amide
fluorescence chemosensors for cyanide anions. The address for the corresponding author
was captured as affiliation for all authors. Please check if appropriate. Saa(2017), doi:
1
0.1016/j.saa.2017.04.008
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ACCEPTED MANUSCRIPT
Two benzoyl coumarin amide fluorescence chemosensors for cyanide anions
a
a
a
a
a,
a
Zian Wang , Qianqian Wu , Jiale Li , Shuang Qiu , Duxia Cao *, Yongxiao Xu ,
b
a
a
Zhiqiang Liu , Xueying Yu , Yatong Sun
a
School of Material Science and Engineering, University of Jinan, Jinan 250022,
Shandong, China
b
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100,
Shandong, China
*
Corresponding author. E-mail address: duxiacao@ujn.edu.cn (D. X. Cao).

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Abstract
Two new benzoyl coumarin amide derivatives with ortho hydroxyl benzoyl as
terminal group have been synthesized. Their photophysical properties and recognition
properties for cyanide anions in acetonitrile have also been examined. The influence
of electron donating diethylamino group in coumarin ring and hydroxyl in benzoyl
groups on recognition properties was explored. The results indicate that the
compounds can recognize cyanide anions with obvious absorption and fluorescence
spectral change and high sensitivity. The import of diethylamine group increases
smartly the absorption ability and fluorescence intensity of the compound, which
allows the recognition for cyanide anions can be observed by naked eyes. The in situ
hydrogen nuclear magnetic resonance spectra combining photophysical properties
change and job’s plot data confirm that Michael addition between the chemosensors
and cyanide anions occurs. Molecular conjugation is interrupted, which leads to
fluorescence quenching. At the same time, there is a certain extent hydrogen bond
reaction between cyanide and hydroxyl group in the compounds, which is beneficial
to the recognition.
Keywords: Coumarin amide; Cyanide anion; Chemosensor; Photophysical property;
Michael addition

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1
. Introduction
For centuries, cyanide because of its extreme toxicity [1-4] has been used as a
poison. In addition to direct ingestion, cyanide vapors and dusts can also enter the
body through the respiratory tract or directly into the skin and produce great harm to
organisms [5]. Cyanide also affects many functions in the human body, including
blood vessels, vision, the central nervous system, heart, endocrine and metabolic
systems. Despite its toxicity, cyanide is still widely applied as industrial materials in
some fields such as synthetic fiber, synthetic resin, herbicide and the gold-extraction
[
6,7]. This enables the detection of trace cyanide to become an important part of
human's health and social environment security [8-11]. So accurate and rapid
determination of cyanide (cyanide anion) is of great significance to environmental
monitoring and food safety.
At present, there are many methods to detect cyanide anions, such as spectral
method, voltammetry, electrochemical method, ion chromatography and so on [12-18].
In recent years, people pay more attention to spectral method with the advantages of
convenient, quick, low cost and high sensitivity [19-28]. Investigation indicates that
hydrogen bonding often can promote the reaction between the Michael receptor and
-
CN , and electron withdrawing group is beneficial to Michael reaction [29,30].
Therefore, here two coumarin amide derivatives with hydroxyl benzoyl as terminal
group were designed and synthesized. The original design is to introduce hydroxyl
synergetic recognition role to cyanide anions. The introduction of diethylamine in
coumarin ring can improve the fluorescence properties of the compound and

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sensitivity of fluorescence recognition.
2
. Experimental
.1. Chemicals and instruments
-hydroxy-benzamide and N,N-diethylaminesalicylaldehyde were purchased
2
2
from Aladdin Reagents. Coumarin-3-carboxylic acid was purchased from Alfa Aesar
company. Diethyl malonate was purchased from Tianjin Kermel Chemical Reagent
Company Limited. Tetrabutylammonium cyanide was used as received from Shanghai
Reagents. Coumarin-3-formyl chloride and 7-N,N-diethylaminecoumarin-3-formyl
chloride
were
obtained
with
coumarin-3-carboxylic
acid
or
7
-N,N-diethylaminocoumarin-3-carboxylic acid and thionyl chloride as the starting
materials according to Ref. [31]. Magnetic resonance spectra were recorded on a
MercuryPlus-400 spectrometer. Mass spectra were recorded on an Agilent
Q-TOF6510 spectrometer.
2
.2. Synthesis and characterization of the compounds
The synthetic routes to the title compounds 1 and 2 are shown in Scheme 1. The
compounds were synthesized by the reaction between coumarin-3-formyl chloride or
-N,N-diethylaminecoumarin-3-formyl chloride and 2-hydroxy-benzamide in
7
anhydrous dichloromethane with triethylamine as catalyzer.
Scheme 1. Synthetic routes to the title compounds 1 and 2.

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2
.2.1. Synthesis of compound 1
Compound 1 was synthesized by the reaction between coumarin-3-formyl
chloride and 2-hydroxy-benzamide. 0.21 g (0.001 mol) Of coumarin-3-formyl
chloride, 0.14 g (0.001 mol) of 2-hydroxy-benzamide and 30 mL of anhydrous
dichloromethane as solvent were put in a 50 mL round bottom flask. And then 0.7 mL
triethylamine as catalyst was added. The mixture was stirred at room temperature for
8
hours and the reaction solution was treated by vacuum filtering. The precipitate was
washed with dilute hydrochloric acid of 1% concentration, then washed with distilled
1
water and dried to get 0.18g white solid compound 1 with 57.5% yield. H NMR (400
MHz, DMSO), δ: 6.98 (t, J = 7.6 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H), 7.45 - 7.50 (m,
2
1
H), 7.54 (d, J = 8.8 Hz, 1H), 7.80 (td, J = 8.0, 1.6 Hz, 1H), 7.85 (dd, J = 8.0, 1.6 Hz,
13
H), 8.04 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 8.94 (s, 1H), 11.57 (s, 1H), 12.44 (s, 1H). C
NMR (100 MHz, DMSO), δ: 116.27, 117.05, 118.39, 118.48, 119.67, 120.10, 125.28,
1
30.59, 131.07, 134.64, 134.68, 148.73, 154.12, 157.00, 159.49, 160.87, 164.27. MS
+
for (M+H) . Calcd exact mass: 310.0637, found 310.0713.
2
.2.2. Synthesis of compound 2
Compound was synthesized similar to compound
2
1
with
7
-N,N-diethylaminecoumarin-3-formyl chloride and 2-hydroxybenzamide as the
1
starting materials with 34.1% yield, yellow solid. H NMR (400 MHz, DMSO), δ:
1
.28 (t, J = 7.2 Hz, 6H), 3.50 (q, J = 7.2 Hz, 4H), 6.54 (d, J = 2.4 Hz, 1H), 6.71 (dd, J
9.2, 2.4 Hz, 1H), 6.98 (t, J = 7.6 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H), 7.48-7.53 (m,
=
1
3
2
H), 7.83 (dd, J = 8.0,1.2 Hz, 1H), 8.84 (s, 1H), 11.95 (s, 1H), 12.67 (s, 1H). C

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NMR (100 MHz, CD Cl), δ: 12.59, 45.53, 96.81, 108.38, 108.93, 110.99, 114.27,
3
119.02, 119.57, 126.86, 132.25, 136.00, 150.60, 153.87, 158.40, 161.08, 163.24,
+
1
63.74, 169.68. MS for (M+H) . Calcd exact mass: 381.1372, found: 381.1487.
2
.3. Structure determination
Single crystal of compound 2 was obtained by slow evaporation of the compound
in the mixed solution of dichloromethane and ethanol. X-ray diffraction data of a
yellow single crystal (0.43 mm × 0.12 mm × 0.064 mm) was collected on a Bruker
Smart APEX-II CCD X-ray single crystal diffractometer. The radiation source was
Mo Ka. The crystal belongs to monoclinic, P2 /a space group with a formula
1
C H N O and molecular weight 380.39. a = 13.8622(12) Å, b = 8.6531(7) Å, c =
21
20
2
5
3
-3
1
0
2
6.3572(13) Å, β = 108.293(9), V = 1862.9(3) Å , Z = 4, ρ = 1.356 g cm , μ =
calc
-1
.809 mm , F(000) = 800.0, R1 = 0.0643, wR2 = 0.2081, T = 293.15 K.
.4. Density functional theory (DFT) calculation
Density functional theory (DFT) calculation on compound 2 was carried out using
Gaussian 09 program. B3LYP level of theory (Becke's three parameter hybrid
functional [32] in conjunction with Lee, Yang, and Parr's correlation functional [33])
was used for the calculation. The frontier molecular orbitals (HOMO and LUMO) of
the compound were obtained using the visualization package Gauss View.
2
.5. Photophysical properties' measurement
UV-vis absorption and steady state fluorescence spectra of the compounds in
-5
-1
-5
-1
acetonitrile with C = 3.0 × 10 mol·L (1) or 1.0 × 10 mol·L (2) at room
temperature were recorded on a Shimadzu UV2550 spectrophotometer and a Horiba
Fluoromax-4 fluorescence spectrometer, respectively. To examine the

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cyanide-recognizing properties of the compounds, tetrabutylammonium cyanide
n-Bu NCN (TBACN) as a cyanide source was added to the solution of compounds 1
4
and 2 in acetonitrile.
3
. Results and discussion
3
.1. Crystal Structure
Molecular structure of compound 2 is shown in Fig. 1. The planarity of
compound 2 is very good with the dihedral angle between the coumarin ring and
benzene ring being only 3.77°, which will be beneficial to fluorescence properties.
The bond lengths of N1-C8 (1.382(5) Å) is longer than that of N1-C7 (1.363(5) Å),
but O3=C8 (1.212(4) Å) is shorter than that of C7=O2 (1.229(4) Å), which may be
because benzoyl group possesses stronger electron accepting ability than diethylamine
coumarin group. The frontier molecular orbitals (HOMO and LUMO) of the
compound is shown in Fig. 2. From Fig. 2, we can see that charge transfer from
diethylamine group to benzamide upon excitation from HOMO to LUMO.
Fig. 1.The molecular structure of compound 2.
Fig. 2. The electron density distribution of the frontier molecular orbitals of
compound 2.
3
.2. Photophysical properties of the compounds
UV-vis absorption and fluorescence spectra of the compounds in acetonitrile are

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4
shown in Fig. 3. The compounds exhibit absorption in violet (1, 305 nm, ε = 1.65×10
-1
-1
4
-1
-1
4
-1
-1
M cm ; 336 nm, ε = 1.38×10 M cm ) or blue (2, 440 nm, ε = 6.14×10 M cm )
spectral region and fluorescence in blue spectral region (1, 417 nm; 2, 483 nm).
Compared with compound 1, the absorption peak of compound 2 has 135 nm red-shift
and molar absorptivity increases about three times. Similar to absorption properties,
compound 2 also exhibits stronger fluorescence emission and longer fluorescence
peak, which is due to the introduction of strong electron donating diethylamino group
enhancing charge transfer of the molecule.
Fig. 3. UV-vis absorption and fluorescence spectra (1, λ = 305 nm; 2, λ =
ex
ex
-5
4
40 nm) of the compounds in acetonitrile with C = 3.0 × 10 mol/L (1) and
-5
1
.0 × 10 mol/L (2).
3
.3. Recognition of the compounds for cyanide anions
UV-vis absorption and fluorescence spectral changes upon the addition of CN to
-
the compounds in acetonitrile are shown in Fig. 4. Both the compounds have sensitive
response to cyanide in acetonitrile. As shown in Fig. 4a, we can see that with the
increase of cyanide, the main absorption peak at 305 nm and 336 nm of compound 1
decrease gradually and three new absorption peaks at 272 nm, 316 nm and 387 nm are
appeared. The complexation is saturated after 1.0 equiv. TBACN was added.
Compound 2 also exhibits obvious spectral change upon the addition of cyanide
anions with original absorption peak disappearing and new absorption peak in short

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wavelength region appearing. Because of the longer absorption peak of compound 2,
the compound exhibits obvious color change from yellow to colorless, which can be
observed by naked eyes (insert of Fig. 4b). Based on the strong fluorescence emission
-
of compound 2, the fluorescence response of 2 to CN was also investigated. As
-
shown in Fig. 4c, because of the complexation with CN , the fluorescence peak of
compound 2 at 483 nm gradually decreases to 18.0% of the original intensity at last,
which can be observed by naked eye (insert of Fig. 4c).
Fig. 4. Changes in UV-vis absorption (a, b) and fluorescence (c, λ = 440
ex
-5
-5
nm) spectra of compounds 1 (C = 3.0 × 10 mol/L) and 2 (C = 1.0 × 10
mol/L) in acetonitrile upon the addition of cyanide anions.
The detection limits [34] of the compounds for cyanide anions were calculated. The
detection limits with absorption as detected signal are 0.025 μM (1) and 0.016 μM (2),
respectively. The detection limit of 2 with fluorescence as detected signal is 0.000047
μM. Compound 2 has higher sensitivity relative to 1. Based on the fact that the
spectral change of compound 2 can be observed by naked eyes because of the longer
absorption and fluorescence peaks and stronger fluorescence emission, the import of
diethylamine is helpful. But the previous reported work found that the import of
diethylamine group decreases the electronegativity of C4 position of coumarin and
then decreases the sensitivity. Most these compounds can recognize cyanide anions
with lower sensitivity [31,35]. So even the compound with diethylamine group

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-
possesses strong fluorescence and can recognize CN with fluorescence as detected
signal and the change can be observed by naked eyes. But the low sensitivity limits
their application. Here it is noted that compound 2 exhibits high sensitivity, which
indicates that ortho hydroxyl benzoyl group is beneficial to the response.
It is generally accepted that high selectivity is a very important criterion for a
desirable chemosensor. Therefore, the influence of other anions on the compounds
-
-
-
-
-
was also examined. As shown in Fig. 5, other anions such as F , Cl , Br , I , H PO ,
2
4
-
-
HSO and SCN all induce negligible absorption changes.
4
-5
Fig. 5. UV-vis spectral changes of compound 2 (C = 1.0×10 mol/L) in
-5
acetonitrile upon the addition of various anions (C = 2.0×10 mol/L).
3
.3. Recognition mechanism
The recognition mechanism of the compounds to cyanide anions was
1
1
investigated based on in situ H NMR. From Fig. 6 we can see that H NMR of
compound 2 has single peaks at 8.86 ppm, 11.98 ppm and 12.69 ppm, which are
attributed to proton in C4 of coumarin (Ha), hydroxyl (Hb) and amino (Hc). After the
addition of TBACN, Ha and Hb peaks disappear and a new peak at 4.91 ppm is
attended. Proton signal of Hc has a slight movement from 12.69 ppm to 13.58 ppm.
The disappearance of proton signal at 8.86 ppm and the appearance of new peak at
4
.91 ppm are due to the Michael addition between cyanide anions and compound 2 at
C4 position, which leads to the double bond on coumarin ring of compound 2 opening

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and cyanide group is added on the β position of the double bond. In addition, the peak
at 11.98 ppm is disappeared after the addition of cyanide anion, which is because
there is a certain extent hydrogen bond reaction between cyanide and hydroxyl group.
1
Fig. 6. H NMR spectra of compound 2 in CD CN before and after the
3
addition of cyanide anions.
In order to clarify the reaction mechanism between the compounds and the
cyanide anion, job-plot curves [36] were also tested. As shown in Fig. 7, the job’s plot
points of compounds 1 and 2 were between 0.6-0.7, which further proved there is a
certain extent hydrogen bond reaction between cyanide anion and hydroxyl group.
Fig. 7. Job’s plot curves of compounds 1 and 2 to cyanide anions.
1
H NMR and job’s plot curves indicate that Michael addition reaction between
the compounds and cyanide anions occurs. And at the same time, the presence of the
hydroxyl group of compounds 1 and 2 makes the hydrogen bonding function
simultaneously. Binding stoichiometry of both compounds with cyanide anion was
calculated according to Ref. [37]. Binding stoichiometries between the compounds
-
and CN are about 1:1, which means one molecule of the compounds bonding with
one cyanide anions and the main reaction site is Michael reaction site C4 in coumarin
group. Binding constants of both compounds with cyanide anion were also calculated

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5
-1
5
-1
according to Refs. [37], which are 1.73 × 10 M (1, absorption), 6.49 × 10 M (2,
5
-1
absorption) and 2.23 ×10 M (2, fluorescence), respectively. The recognition
mechanism is shown in Fig. 8.
-
Fig. 8. Proposed bonding mechanism of compound 2 to CN .
There is an interesting phenomenon that after the addition of cyanide anions,
absorption band of compound 2 is similar to the long wavelength absorption band of 1.
-
We think that before the addition of CN , the absorption spectra of the compounds are
mainly from charge transfer. Diethylamine is a strong electron donating group. The
import of this group in compound 2 increases the electron density of the molecule and
leads to obvious charge transfer from diethylamine group to benzamide and then
-
further leads to longer absorption and fluorescence band. After the addition of CN ,
the double bond on coumarin ring is broken and this charge transfer is blocked. The
role of diethylamine group is weakened. So the main absorption spectra of the two
compounds are similar.
4
. Conclusion
Two benzoyl coumarin amide fluorescence chemosensors for cyanide anions
have been synthesized. The compounds were characterized by nuclear magnetic
resonance spectroscopy and mass spectrometry, and the crystal structure of compound
2
was obtained. Both the compounds exhibit obvious UV-vis absorption and

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fluorescence response for cyanide anions in acetonitrile. Especially, compound 2
exhibits obvious color and fluorescence change, which can be observed by naked eye.
Both the compounds can response cyanide anions with high sensitivity. Identification
mechanism analysis shows that the compounds and cyanide anions have a Michael
addition effect, and the conjugation of the molecules is interrupted, which leads to the
fluorescence quenching. There is a certain extent hydrogen bond reaction between
cyanide and hydroxyl group, which is beneficial to the recognition.
Acknowledgements
This work was supported by the National Natural Science Foundation of China
(21672130, 51373069) and the Natural Science Foundation of Shandong Province
(ZR2015BL011), Key Research and Development Plan of Shandong Province
(2016GSF117004), Colleges and Universities Science and Technology Foundation of
Shandong Province (J16LA08) and the Fund of Graduate Innovation Foundation of
University of Jinan, GIFUJN (S1504).
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Fig. 1.The molecular structure of compound 2.

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Fig. 2. The electron density distribution of the frontier molecular orbitals of
compound 2.

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Fig. 3. UV-vis absorption and fluorescence spectra (1, λ = 305 nm; 2, λ = 440 nm)
ex
ex
-5
-5
of the compounds in acetonitrile with C = 3.0 × 10 mol/L (1) and 1.0 × 10 mol/L
2).
(

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Fig. 4. Changes in UV-vis absorption (a, b) and fluorescence (c, λ = 440 nm) spectra
ex
-5
-5
of compounds 1 (C = 3.0 × 10 mol/L) and 2 (C = 1.0 × 10 mol/L) in acetonitrile
upon the addition of cyanide anions.

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-5
Fig. 5. UV-vis spectral changes of compound 2 (C = 1.0×10 mol/L) in acetonitrile
-5
upon the addition of various anions (C = 2.0×10 mol/L).

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1
Fig. 6. H NMR spectra of compound 2 in CD CN before and after the addition of
3
cyanide anions.

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Fig. 7. Job’s plot curves of compounds 1 and 2 to cyanide anions.

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Fig. 8. Proposed bonding mechanism of compound 2 to CN .

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Scheme 1. Synthetic routes to the title compounds 1 and 2.

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Graphical Abstract

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Highlights
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Two benzoyl coumarin amide derivatives with hydroxyl benzoyl group were
synthesized.
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The compounds can recognize CN with obvious absorption and fluorescence
spectral change.
The change of the compound with diethylamine group can be observed by
naked eyes.
The recognition mechanism is Michael addition assisted by hydrogen bonding
reaction.