One diethylamine coumarin derivative with nitro substituted chalcone structure as chemosensor for cyanide and copper ions

Article abstract of DOI:10.1016/j.inoche.2015.06.031

Abstract One diethylamine coumarin derivative with nitro substituted chalcone structure was synthesized via typical condensation reaction between 4-nitro-2-(hydroxyl)acetophenone with 7-(diethylamino)coumarinaldehyde in good yields. The investigation indi

Full text of DOI:10.1016/j.inoche.2015.06.031

Inorganic Chemistry Communications 59 (2015) 68–70
Contents lists available at ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
One diethylamine coumarin derivative with nitro substituted chalcone
structure as chemosensor for cyanide and copper ions
a
Yanyan Shan a, Yunhui Sun b, Ning Sun a, Ruifang Guan a, Duxia Cao a, , Kangnan Wang ,
⁎
Qianqian Wu a, Yongxiao Xu a
a
School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong, China
b
Zhejiang Province Institute of Multipurpose Utilization of Alunite, Wenzhou 325028, Zhejiang, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 May 2015
Received in revised form 28 June 2015
Accepted 29 June 2015
Available online 3 July 2015
One diethylamine coumarin derivative with nitro substituted chalcone structure was synthesized via typical
condensation reaction between 4-nitro-2-(hydroxyl)acetophenone with 7-(diethylamino)coumarinaldehyde
in good yields. The investigation indicated that the compound exhibits quickly obvious UV–vis absorption,
color change and fluorescence response to cyanide and copper ions in acetonitrile conditions. The bonding
mechanism based on spectra change and in situ 1H NMR suggested that cyanide is bonded to 4-position of
coumarin and 1:2 complexation between compound and copper ion forms.
Keywords:
Coumarin derivative
Chalcone
© 2015 Elsevier B.V. All rights reserved.
Copper ion
Cyanide anion
Chemosensor
For the past few years, due to the important roles in biological,
industrial and environmental processes of cyanide and copper ions,
the study of optical chemosensors for cyanide [1–10] and copper ions
[11–16] has attracted more and more attention of many chemists. As
we all know, cyanide is a highly toxic compound and the lethal to
human is minimal [17]. Even though it has high toxicity, cyanide is real-
ly an important raw material in many industrial fields such as synthetic
resin, pharmaceuticals, pesticides, insecticides, and fertilizers [18–20].
Copper, a very important element for hemopoiesis, metabolism, growth
and immune system [21], has indispensable functions in various biolog-
ical processes. But when the copper ion concentration is out of the re-
quired range, the normal activities of life system would be disrupted
and the cells would be poisoned, which would cause severe copper met-
abolic disorders [22–24]. As a progress of our group in chalcone deriva-
tive as chemosensors for cyanide, one diethylamine coumarin
derivative with nitro substituted chalcone structure was synthesized
and its recognition properties for cyanide and copper ions were
reported.
nitro group was also synthesized. The molecular structures of
compounds 1 and R1 are shown in Fig. 1.
To examine the recognizing properties of the compounds for cyanide
and copper ions, tetra (n-butyl)ammonium cyanide (TBACN) and
copper (II) perchlorate hexahydrate (Cu(ClO4)2·6H2O) as cyanide
and copper ion sources, respectively, were added to a solution of
the compound in acetonitrile. The compound exhibits fast response
to cyanide and copper ions (b5 s). As shown in Fig. 2a, with the
increase of cyanide anions, the absorption peak of compound 1 at
489 nm (ε = 3.19 × 104 M−1 cm−1) decreases gradually and is
blue shifted to 469 nm with an isoabsorptive point at 481 nm. Obvi-
ous color change from red to yellow is observed. As shown in Fig. 2b,
upon complexation with Cu2+, the strong absorption peak at 489 nm
gradually decreases, at the same time, a weak absorption band at
395 nm was formed. The compound also exhibits obvious color
change from red to claret.
The fluorescence spectra changes of compound 1 upon the addition
of CN− and Cu2+ in acetonitrile were also detected. As shown in Fig. 3
and Fig. S1, red fluorescence at 669 nm was completely quenched and
fluorescence change also can be observed by naked eye. Similar com-
pound without nitro group R1 also exhibits obvious response to cyanide
anions, but the response rate is slow and sensitivity is less (Fig. S2a),
which indicates that the import of nitro group is beneficial to the
response for cyanide anions. Compound R1 exhibits similar response
to copper ions (Fig. S2b) with the original absorption peak (475 nm)
decreasing gradually and disappearing at last, at the same time, a
weak absorption peak at 395 nm appearing and increasing gradually.
The title compound 1 was synthesized by condensation reaction
between
7-(diethylamino)coumarinaldehyde
and
4-nitro-2-
(hydroxyl)acetophenone with a yield of 50% in ethanol (Scheme S1)
and the compound was characterized by 1H NMR, 13C NMR and ESI-
mass spectrometry [25]. A corresponding compound R1 without
⁎
Corresponding author.
E-mail address: duxiacao@ujn.edu.cn (D. Cao).
http://dx.doi.org/10.1016/j.inoche.2015.06.031
1387-7003/© 2015 Elsevier B.V. All rights reserved.

Y. Shan et al. / Inorganic Chemistry Communications 59 (2015) 68–70
69
Fig. 1. The molecular structures of compounds 1 and R1.
What needs to be noted is that the absorption spectra of compounds 1
and R1 are similar after complexing with copper ions, which indicates
that the original main absorption peak is broken and the new absorp-
tion peak may be derived from diethylamine coumarin group.
Besides, job plots of the compound for cyanide and copper ions were
also detected. As shown in Fig. 4(a), job plot data indicates that 1:1
reaction between the compound and cyanide anion occurs. Bonding
mechanism of the compound for cyanide anions was investigated
using the in situ 1H NMR spectra of the compound before and after
the interaction with CN− in CD3CN. As shown in Fig. S3, the proton sig-
nal of 4-coumarin group at 8.23 ppm disappeared and peaks related to
vinylic protons (7.91(d, J = 14.8 Hz, 1H), 8.21(d, J = 15.6 Hz, 1H)) did
not disappear and only the position changed (7.68(d, J = 15.2 Hz,
1H), 8.82(d, J = 15.6 Hz, 1H)), which indicates that the possible bonding
mechanism is cyanide anions being bonded to 4-coumarin. The bonding
of CN- to 4-coumarin induces to the breaking of intramolecular charge
tranfer and then results in the decrease of fluorescence.
Job plot data (Fig. 4(b)) indicate that 1:2 complex between the com-
pound and copper ions forms. Compound R1 also exhibits similar com-
plexation to copper ions (Fig. S5), which indicates nitro group dose not
take part in the complexation. The possible mechanism of the com-
pound for copper ions is shown in Fig. S6. Hydroxyl and two carbonyl
groups complex with two copper ions to form 1:2 complex. The de-
crease of fluorescence caused by Cu2+ may be derived from
the intramolecular photoinduced electron transfer from the excited
fluorophore to copper ion [26].
can induce obvious change of absorption spectra, but the change is dif-
ferent to that of Cu2+, which indicates that the compound can recognize
Fe3+ and Cu2+ at the same time with absorption as detected signal.
Fe3+ cannot cause obvious color change of the compound and then
the compound can recognize Cu2+ with high selectivity using color
change.
In summary, the effectiveness of one coumarin nitro substituted
chalcone derivative as chemosensor for cyanide anions and copper
ions was demonstrated. The results indicated that the compound
exhibits obvious UV–vis absorption, color and fluorescence response
in acetonitrile solution. Bonding mechanism investigation indicates
that cyanide is bonded to 4-position of coumarin, hydroxyl and two
carbonyl group complexes with two copper ions to form 1:2 complex.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (20802026, 50803033, 51373069), and the Natural
The detection (LOD) [27,28] and quantification (LOQ) limits of the
compound for CN− and Cu2+ in acetonitrile with absorption and
fluorescence as detected signals are also examined (Table S1, Figs. S7
and S8). LODs with fluorescence as detected signal are 0.018 μM and
0.004 μM for CN− and Cu2+, respectively.
The influence of other cations and anions on the response of
compound to copper ions and cyanide anions was examined. As
shown in Fig. S9 and S10, the compound exhibits good selectivity.
Other anions such as Cl−, Br−, I−, SCN−, and HSO−4 and cations such
as Na+, Mg2+, Co2+, Ni2+, Ca2+, and Zn2+ induce negligible absorption
changes to the compound, which indicates that the compound can
recognize CN− and Cu2+ from these anions and cations. Even Fe3+
Fig. 3. Fluorescence (C = 10 μM) spectra change of compound 1 upon the addition of CN−
in acetonitrile.
Fig. 2. UV–vis absorption spectra change of compound 1 upon the addition of CN− (a, C = 10 μM) and Cu2+ (b, C = 20 μM) in acetonitrile. (For interpretation of the references to color in
this figure, the reader is referred to the web version of this article.)

70
Y. Shan et al. / Inorganic Chemistry Communications 59 (2015) 68–70
Fig. 4. Job's plots of the compounds for cyanide anions (a) and copper ions (b).
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Appendix A. Supplementary material
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.inoche.2015.06.031.
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