A highly sensitive and selective fluorescent turn-on chemosensor bearing a 7-diethylaminocoumarin moiety for the detection of cyanide in organic and aqueous solutions

Article abstract of DOI:10.1039/d0nj03003a

New Schiff bases bearing a salicylidene moiety with different substituents and 7-diethylaminocoumarin-thiazole were synthesized and characterized using spectroscopic methods. Also, four of the synthesized compounds (4, 6, 7, and 9) were characterized using X-ray analysis. The chemosensor properties of the compounds (4-9) were investigated using UV-vis and fluorescence spectroscopy as well as visual changes, and it was found that the compounds except 7 showed selectivity to cyanide anions in both organic and aqueous solutions, observed by the drastic increment in emission intensity. The mechanism of interaction between the cyanide anions and imine carbon at the Schiff base was determined using the 1H NMR titration method. The determination of the thermal stability of the compounds was performed using thermogravimetric analysis (TGA). Density Functional Theory (DFT) calculations were also employed to gain insights into the experimental data. This journal is

Full text of DOI:10.1039/d0nj03003a

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Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
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A highly sensitive and selective fluorescent turn-on chemVie
w
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DOI: 10.1039/D0NJ03003A
bearing 7-Diethylaminocoumarin moiety for detection of cyanide in
organic and aqueous solutions
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a,b
c
Burcu AYDINER , Ömer ŞAHiN , Deniz ÇAKMAZ , Gökhan KAPLAN , Kerem KAYA , Ümmühan
a
d
a
DOI: 10.1039/x0xx00000x
ÖZMEN ÖZDEMİR *, Nurgül SEFEROĞLU , Zeynel SEFEROĞLU *
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New Schiff bases bearing salicylidene moiety with different substituents and 7-Diethylaminocoumarin-thiazole were
synthesized and characterized by spectroscopic methods. Also, four of the synthesized compounds (4, 6, 7, and 9) were
characterized by X-ray analysis. Chemosensor property of compounds (4-9) were investigated by UV-vis and fluorescence
spectroscopy as well as visual changes, and the compounds except 7 found that they showed selectivity to cyanide anion in
both organic and aqueous solution by observed drastic increment at emission intensity. The mechanism of interaction
between cyanide anion and imine carbon at the Schiff base was determined by the 1H NMR titration method. The
determination of the thermal stability of the compounds was performed by TGA. The Density Functional Theory (DFT)
calculations were also employed to gain insight into the experimental data. Furthermore, the most stable tautomeric form
was determined by DFT.
Fast response time, high sensitivity, and low cost make the
fluorescent chemosensors preferable methods in anion
detection. Azine, azo, benzimidazole, benzothiazole, BODIPY,
calixarene, imine, indole, fluorine, fluorescein, malononitrile,
naphthalene, naphthalimide, pyrene, quinoline, and coumarin
based fluorescent chemosensors have been designed and used
Introduction
Anions are a class of chemicals that can play a crucial role in
many processes in industries and an uncontrollable level of
anions can cause many problems especially on human health.
1
6,7
in different applications for many years. Coumarin based
For example, cyanide is known as poison and can be found
naturally in the plants: apricot kernel, cassava roots, bamboo
shoots, almond and sprouting potato which is called cyanogenic
fluorescent chemosensors have been designed not only for
-
-
-
-
-
3+
anions (CN , F , ClO , HSO
3
, Cl , and etc.) but also cations (Al ,
2+
2+
2+
3+
Cu , Zn , Hg , Fe , and etc.), and small molecules (Cysteine,
H S, H O , and etc.). The mechanism of ion sensing is generally
2 2 2
2
glycosides. Furthermore, hydrogen cyanide and cyanides are
9
commonly used in silver and gold mining, production of dyes
depending on increasing or decreasing/quenching of the
fluorescent intensity. The classical sensing mechanisms are
photoinduced electron transfer (PET), intramolecular charge
transfer (ICT), fluorescent resonance energy transfer (FRET),
hydrogen bonding, metal-ligand charge transfer (MLCT),
excimer/exciplex formation, exited state intra-/intermolecular
proton transfer (ESIPT), and nucleophilic substitution
3
and plastics. Cyanide reacts with iron in the cytochrome
oxidase, which is the key enzyme of the respiratory system, and
it blocks the cytochrome oxidase activity. Not only the
cytochrome oxidase but also the other enzymes: glutamate
decarboxylase, xanthine oxidase, superoxide dismutase, NO
synthase, and nitrite reductase are inhibited in the presence of
cyanide ions.3
-5
2,7,9
reactions.
Detection of the anions is crucial because of all the reasons
mentioned above, therefore, there are various detection and
determination
Schiff bases containing coumarin-thiophene-salicylidene
moieties have been designed, synthesized, and applied for
sensing specifically toward CN , F , AcO , H PO anions and
2 4
reported by our group. In a study conducted by our group, we
investigated series of coumarin-thiophene core Schiff based
chemosensors that are capable of recognizing CN ion with
remarkable selectivity in an aqueous solution, although using
only organic media as DMSO, resulted in fluorescence
increasing without selectivity. In this study, we investigated
the effect of the thiazole ring by using as π-bridge/acceptor,
instead of the thiophene ring that previously used (Fig. 1). Our
methods
developed
such
as
Ion
-
-
-
-
Chromatography-Pulsed
Amperometry
(IC-PAD),
Gas
10
Chromatography-Mass Spectroscopy (GC-MS), polarography,
High-Performance Liquid Chromatography-Ultraviolet (HPLC-
UV), capillary electrophoresis, electrochemistry, sol-gel
-
6
transition method, colorimetry, chemosensors, and etc.
10
a. Department of Chemistry, Faculty of Science, Gazi University, Yenimahalle, Ankara
0
6560, Turkey. ummuhan@gazi.edu.tr, znseferoglu@gazi.edu.tr
b.
c.
d.
Sanko Tekstil Işletmeleri Sanayi ve Ticaret A.S. Isko Sb, Organize Sanayi Bölgesi results showed that thiazole ring increased the selectivity
3.Cadde, İnegöl, BURSA 16400, Turkey.
towards cyanide in both organic and aqueous solution.
Department of Chemistry, Faculty of Science and Letters, Istanbul Technical
University, Istanbul 34469, Turkey.
Department of Advanced Technology, Gazi University, Yenimahalle, Ankara 06560,
Turkey.
Moreover, we improved the coumarin ring’s fluorescent
properties by adding the diethylamino group to 7-position of
the coumarin moiety. Previous studies show that when
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary unsubstituted coumarin based Schiff bases interact with
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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cyanide, it gave the light-up effect but very low comparing our Absorption and emission properties
present study.11 And the effect of the substituents at
salicylidene moiety on the light-up effect also investigated and
observed that strong electron-donating groups at the para-
position of salicylidene ring blocking/quenching fluorescence
effect. Colorimetric and fluorimetric properties of compounds
were determined by using the absorption and fluorescence
spectroscopic techniques as well as naked-eye. Ion sensing
studies were also performed at different pH (6 to 11) in the
DMSO-water binary solution. Thermal gravimetric analysis
View Article Online
DOI: 10.1039/D0NJ03003A
Synthesized compounds 4-9 are colored solid molecules that
are a different shade of yellow. Their absorption and emission
spectra were measured in four aprotic solvents with different
T
polarities; tetrahydrofuran (THF, E :0.21), dichloromethane
(
DCM, E
T
:0.31),
T
dimethylformamide (DMF, E :0.38), and
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dimethylsulfoxide (DMSO, E
T
:0.44). Absorption and emission
spectra of the compounds can be seen in Figs. 2 and S34 - S38.
The absorption maxima of the compounds were between 400
nm and 450 nm in the visible region, and emission maxima
ranging from 465 to 504 nm (Table 1). Absorption maxima of
the compounds did not show a regular correlation with the
increase of solvent polarity while emission maxima slightly
shifted to bathochromic region. The effect of the substituent at
salicylidene moiety on fluorescence features was investigated
and a significant difference was observed at 7 that gave longer
absorption and emission wavelengths, due to the presence of
(TGA) was conducted to determine the thermal stability of all
synthesized compounds. Interaction mechanisms were
investigated by H NMR spectroscopy and supported by DFT and
TD-DFT theoretical studies. In addition, the structural
characterization of compounds was confirmed by spectroscopic
methods and molecular characterization of four compounds
were also determined by X-ray structural analysis.
1
2
diethylamino as a strong electron-donating group (NEt ) at 4-
position of salicylidene moiety. Also, 7 has two absorption
bands in all solvents used while others have a shoulder at a
lower wavelength to absorption maxima in only THF and DCM
(
Table 1). While the origin of the lower wavelength bands of the
compounds is 7-Diethylaminocoumarin-thiazole group, the
higher wavelength bands are salicylidene moiety due to n-π*
transition. Also, these results are supported by a theoretical
study (see Computational Analysis section).
Fig. 1. The structure of compounds (4-9)
Results and discussion
Synthesis
The compounds (4-9) were obtained in moderate yields (60-77
%
) and the synthetic approach is depicted in Scheme 1. The
structures of the synthesized compounds were confirmed by
1
13
FT-IR, H/ C NMR, and HRMS (in ESI). Also, crystal structures of
compounds 4, 6, 7, and 9 were determined and discussed X-ray
analysis section.
O
O
CHO
CuBr2, EtOH
MW, 2 min. 80 oC
O
O
Cat. Pip.
EtOH, r.t.
CH3
CH2Br
+
Et2N
OH
O
Et2N
O
1
O
Et2N
O
2
O
S
EtOH
H2N
NH2
Fig. 2. Absorption (20 µM in DMSO) (left) and emission (2 µM in DMSO) (right)
spectra of 5 in different polarity solvents (Normalized absorption and emission
spectra are in above).
NH2
R3
CHO
R2
N
O
S
N
OH
+
R2
Cat. Acetic acid
N
S
EtOH, 
Et2
N
O
HO
0-77 %
(71%)
R1
R3
R1
Et2N
O
O
3
6
R1: H, OMe
R2: H, OMe, NEt2
R3: H, Me, Cl
(4) R1: H, R2: H, R3:H
(5) R1: OMe, R2: H, R3:H (75%)
(6) R1: H, R2: OMe, R3:H (65%)
(7) R1: H, R2: NEt2, R3:H (60%)
(
(
8) R1: H, R2: H, R3Me (77%)
9) R1: H, R2: H, R3:Cl (65%)
Scheme 1. Synthetic pathways for the compounds (4-9)
2
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Table 1. Absorption and emission maximum values of 4-9 in different solvents.
THF DCM DMF DMSO
Table 2. Absorption maxima of the compounds (4-9) in the absen
of cyanide
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DOI: 10.1039/D0NJ03003A
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b
fl
λ
abs
λ
fl
λ
abs
λ
fl
λ
abs
λ
fl
λ
abs
λ
Absence of CN-
After addition of 20 equiv. CN-
Compound
(nm)
(nm)
465
(nm)
400(s),
25
400(s),
30
(nm)
472
(nm)
420
(nm)
483
(nm)
435
(nm)
481
λabs (nm)
λ
abs (nm)a
4
5
6
7
8
9
415
4
5
6
7
8
9
435
425
425
400, 450
420
420, 484
425, 503
425, 485
4
415
466
468
472
467
468
473
473
473
472
473
425
425
483
484
504
483
483
425
425
480
480
500
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480
4
b
400, 450
420, 510
420, 520
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385(s),
420
390(s),
430
425
395,
400,
445
400,
445
420
405,
450
420
a
b
Underlined wavelengths are the observed new bands after addition of cyanide. no
changes observed.
4
40
400
400,
4
35
395(s),
395(s),
425
425
4
20
430
a
Absorption maxima, c: 20 µM; b Emission maxima, c: 2 µM. (s) shoulder
Spectrophotometric and spectrofluorimetric determination of ions
in organic and partial aqueous media
-
The sensitivity and the selectivity of the competing anions (F ,
Cl , Br , I , AcO , CN , HSO
-
-
-
-
-
-
-
-
4 3 2 4
, NO , and H PO ) towards the 4-9
have been investigated to determine the chemosensor
properties of compounds. The anion interaction and the sensing Fig. 3. Absorption spectra (20 µM in DMSO) (left) and emission spectra (2 µM in
DMSO) (right) of 5 after addition of 20 equiv. of all the anions. Insets: Color
ability of the compounds were performed by using (ambient light) and fluorescence (λex. 365 nm) change after addition of 20 equiv
of anions.
spectrophotometric (20 µM) and spectrofluorimetric (2 µM)
titration methods in DMSO (Figs. 3 and S39-S43). As shown in
All chemosensors except 7 gave a similar response to
-
-
Fig. 3, upon addition of the various anions to the 5, only F , AcO ,
cyanide as strongly increased fluorescence intensity but the
addition of the other anions did not affect the fluorescence
intensity at maxima. The only exception was observed with 8
that upon addition of fluoride, a new band appeared at 570 with
a weak emission.
-
-
CN and H
PO
2 4
interacted and new absorption bands were
obtained at 503 nm. More importantly, drastically increased
was observed in emission of 5 only for cyanide anion. Titration
spectra of 5 with cyanide was given in Fig. 4 and showed
fluorescence intensity increased as 5-fold. A similar trend at
absorption and emission spectra was observed with the others
(4, 6, 8 and 9) except 7 (Figs. S39-S43). Chemosensor 7 did not
give any spectral changes upon the addition of the anions. This
phenomenon can be explained that 7 has a strong electron
donor group as diethylamino at 4-position of the phenyl ring,
which was caused by increment electron density at imine
carbon and hydroxyl group to hinder addition. A similar
phenomenon was observed in our previous study when the
dihydroxyl group at phenyl ring was obstructed the addition
proses at imine carbon. Changes at the absorption maxima of
the compounds after the addition of 20 equiv. cyanide is
depicted in Table 2. After the addition of cyanide, the
substituent groups, 3- and 4-methoxy, 5-chloro, and 5-methyl,
at salicylidene moiety showed a significant effect on the
1
3
Fig. 4. Emission spectra (2 µM in DMSO, λex. 425 nm) of 5 after addition of up to
20 equiv of cyanide.
2
absorption maximum except 4-NEt . The most significant shift
was observed for 4 (unsubstituted derivative of Schiff base) that
absorption maxima gave a hypsochromic shift from 435 nm to
Photographs of anion interaction of the chemosensors were
also taken under ambient and UV-light to determine naked-eye
detection. Each of the chemosensors showed a coloration
4
20 nm. Interestingly, chemosensors 5 and 6 bearing electron
-
-
-
response to F , AcO and CN changing from yellow to light red
donor methoxy substituent interacted with F-, AcO- and CN-,
while diethylamino bearing 7 didn't interact.
-
or orange except 7 while they only responded to CN as
increased emission intensity/brightness except 5 and 8 which
their emission color changed from green to orange with the
-
-
-
addition of F and AcO . Meanwhile, the other studied anions (Cl
-
-
-
-
-
, Br , I , HSO
4
, NO
3
, and H PO
2 4
) showed no absorption or
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emission color changes, and the results are illustrated in Figs. 3 caused new absorption bands at the bathochromic region while
and S39-S43 insets.
To examine the potential application of the compounds as except 5 at pH 11 was a high intensity increasing (Figs. S53-57).
chemosensors (4, 5, 6, 8 and 9), titration experiments were also
View Article Online
DOI: 10.1039/D0NJ03003A
fluorescence intensities of sensors did not change significantly
In addition, the sensitivity of chemosensors toward the
in partial aqueous solution as cations that are present of many biological and environmental
-
-
-
-
done with F , AcO , CN and H
2
PO
4
9
:1, DMSO: water (v/v). As depicted in Figs. 5 and S44 - S47, only processes were also investigated with the alkali, alkaline-earth,
-
+
2+
2+
2+
CN responded towards the chemosensors in aqueous media transition, and post-transition metal ions; K , Mg , Cd , Co ,
-
-
-
2+
2+
3+
2+
2 4 2
while the other anions (F , AcO , and H PO ) interacting with Ni , Hg , Al , Sn . The sensitivity study of cations was done
0
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chemosensors in DMSO, did not show any significant change in in a basic medium by adding 10 equiv of TBAOH to sensors in
the spectral properties. Upon addition of cyanide anions, DMSO. This caused deprotonation of the hydroxy proton in the
absorption maxima of chemosensors shifted to blue, 5-10 nm salicylidene moiety and new absorption bands were observed
while fluorescence intensity of chemosensors increased. at 485-518 nm (Figs. S58-63). Then, ligand-metal interactions
Furthermore, while there was not any color alteration under the were investigated by adding 20 equiv. of cations to mixed
ambient light, the emission color became brighter under UV solution of the compounds, by UV-vis spectroscopy. After the
+
2+
3+
light.
addition of up to 20 equiv of K , Mg , Al , no significant
spectral changes in absorption were observed (4-9). However,
2
+
2+
2+
when especially transition metals (Cd , Co , Ni ) were added
at the same amount, the absorption band of sensors were
shifted hypsochromicly (410-430 nm).
These results can be attributed to the charge transfer from
ligand to transition metal cations (LMCT) which is significantly
larger and leads to more active/attractive than the alkali metal
and alkaline earth metal cations. It was expected that the scope
of the conjugation of the whole system will be greater at
interactions with transition metals. In addition, it has been
known that the interactions of only the double electrons of the
deprotonated oxygen atom in the phenyl ring are much
1
4
Fig. 5. Absorption spectra (20 µM) (left) and emission spectra (0.2 µM) (right) of
5
after addition of 50 equiv of the anions in 9:1, DMSO:water (v/v). Insets: Color stronger than the oxygen atom in the coumarin ring. Therefore,
(
ambient light) and fluorescence (λex. 365 nm) changes after addition of 50 equiv
of anions.
the phenol group binds more easily with the metal cation than
1
5
the coumarin due to stronger affinity. Transition metals also
interact with the nitrogen atom in the imine group of Schiff
bases. Observed hypochromic shifts in the absorption spectra
were caused by the interaction of compounds with the
transition metal cations through the phenyl oxygen atom and
imine nitrogen atom to form chelates that made the stable ring
formation on the complex. As a result, although there was
strong interaction between compounds and the transition
metals, any selectivity toward metal cations did not observe.
The interference of other anions in the determinations of
cyanide has been studied in detail. The results are depicted in
Fig. 6. These studies were carried out using potential interfering
-
-
-
anions as F , AcO , and H
2
PO
4
in the same concentration range
-
with CN (with the addition of 50 equiv of each anion) (Figs. S48-
5
2). It is gratifying to note that studied anions have no
significant interference with cyanide.
Sensing mechanism
The chemosensors (except 7) showed excellent selectivity
towards cyanide in both organic solvent (DMSO) and partial
aqueous solution with an increment of fluorescent. While the
absorption spectra of chemosensors showed that the
interaction with F , AcO and CN , fluorescence only changed
with CN . These results indicated that there is two interaction
-
-
-
-
mechanism between anions and chemosensors. Interacted
-
-
-
anions, F , AcO and CN , are more basic than other studied
anions and expected the deprotonate hydroxyl hydrogen at
phenol moiety. Deprotonation of hydroxyl caused new
absorption bands at the bathochromic region (450-520 nm) at
absorption spectra. The formation of new absorption band
might likely be due to the formation of the phenoxide group,
which is more pronounce electron donor than the phenol
group. Although deprotonation in process, this does not explain
increased fluorescence intensity with only cyanide at the
-
-
-) with CN- in 9:1,
Fig. 6. Interference studies of other anions (F , AcO , and H PO
DMSO:water (v/v).
2 4
Moreover, the pH effect of the media for chemosensors
were studied in mixtures of DMSO and buffer (9:1, v/v).
Absorption spectra of chemosensors showed that after pH 9,
4
| J. Name., 2012, 00, 1-3
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Page 5 of 13
Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
emission spectra. Cyanide has both nucleophilic and basic
properties. Therefore, the second mechanism can be caused by
the addition of cyanide to imine carbon. Both mechanisms are
given in Scheme 2. The nucleophilic addition of cyanide also
explained why only cyanide interacted in partial aqueous
media. Cyanide has low hydration energy while the basicity of
the other anions is significantly decreased due to the formation
of a hydrogen bond between the anions and water molecules.
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Addition Mechanism
CN-
View Article Online
DOI: 10.1039/D0NJ03003A
H2
H3
H2
H3
H2'
H1
H5'
H6'
NC H1'
H3'
H5
H1
H5
S
H7'
H9'
S
H7
H6
S
H7
H6
O
H4
H4
N
H8'
N
H
H4'
OCH3
CN-
H8
N
C
N
-
,
F
-
H8
N
N
N
O
HO
OCH3
OCH3
O
Et2N
O
O
Et2N
O
O
Et2N
O
CN-
F-
H9
H9
Deprotanation Mechanism
Scheme 3. Possible mechanism of anions interaction with the compounds (5 was
1
used as a reference) based by H NMR titration study.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Scheme 2. Proposed sensing mechanisms of the anions.
1H NMR experiments were undertaken to gain further
insight and determinate to the anion binding interaction of the
compounds. 5 was selected as a reference chemosensor and
1
Fig. 7. H NMR spectral change of 5 (10ꢀmM) in the absence (a) and presence of 2
6
equiv of TBACN (b), and TBAF (c) in DMSO-d .
-
-
titration study was done with F and CN anions in DMSO-d
and Scheme 3). Upon addition of fluoride, OH signal was
disappeared, imine (H ), thiazole (H ), and phenyl protons (H
, and H ) were shifted to the upper field. These shifts indicate
6
(Fig.
7
X-ray analysis
1
5
2
,
H
3
4
deprotonation of OH proton that causes increased charge
density to strengthening the shielding effect in the conjugated
system. As expected no significant change observed at
coumarin rings signals. Also, after the addition of 2 equiv. of
The single crystals of 4, 6, 7, and 9 with dimensions were
grown by slow evaporation of their chloroform solution. The
crystals were first mounted on a micro amount and then
attached to a goniometer head on a Bruker D8 VENTURE
diffractometer equipped with PHOTON100 detector and
measured with graphite monochromated Mo-Kα radiation (λ =
.71073 Å) using 1.0° of Ω and ϕ rotation frames at room
temperature. The structures have been solved by intrinsic
method SHELXS-1997 (Sheldrick, 1997) and refined by SHELXL-
fluoride, a new peak as triplet at 16.15 ppm (120.2 Hz)
-
appeared, indicating the formation of [HF
2
] species.
-
Within addition of 2 equiv of CN , OH signal disappeared, all
signals shifted slightly to upper field and the new signal at 5.95
0
1
ppm appeared while imine (H ) proton at 9.37 ppm was mostly
diminished, more importantly, a new peak at 5.24 ppm
appeared which is consisting of the addition of cyanide to imine
16,17
2
014/7 (Sheldrick, 2014).
All the molecular drawings are
18
generated using OLEX2. Ver. 1.2-dev. Thermal ellipsoids for all
the structures are plotted in Fig. S64. Fig. 8 shows the crystal
packing of the structures and Fig. 9 shows π—π interaction. The
crystal data and structure refinement parameters for all the
structures are given in Table 3. Table S33 gives the
intramolecular hydrogen bonding parameters for all the
structures. CCDC 1975395, 1975396, 1975398, and 1975393
contain the supplementary crystallographic data for 4, 6, 7, and
carbon (H
thiazole (H
1
’) (Scheme 3). Unlike fluoride titration results,
) proton and phenyl protons (H , H , and H ) were
5
2
3
4
showed significant shifts to the upper field. Furthermore, all
coumarin signals shifted to the upper field. All these upper field
shifts supported two different mechanisms as deprotonation
and addition. NMR titration result showed major product was
cyanide addition to imine carbon. The sensing mechanism also
explained by theoretical study (see Computational Analysis
section).
9
, respectively. Further details on crystal data, data collection,
and refinements can be found on the supporting information.
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 6 of 13
ARTICLE
Journal Name
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Table 3. Crystal data and structure refinement parameters for 4, 6, 7, and 9
View Article Online
DOI: 10.1039/D0NJ03003A
4
6
7
9
Empirical
formula
Formula
weight
C
23
H
21
N
3
O
3
S
24
C H
23
N
3
O
4
S
27
C H
30
N
4
O
3
S
24 23 3 3
C H N O S
419.49
449.52
490.61
433.51
(g/mol)
T(K)
304(0)
305(0)
311(0)
303(2)
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
λ(Å)
0.71073
0.71073
0.71073
0.71073
Crystal
triclinic
P-1
triclinic
P-1
triclinic
P-1
triclinic
P-1
system
Space group
Unit cell
dimensions:
(Å, º)
a
b
c
8.4790(7)
8.0871(5)
8.3785(5)
7.6487(14)
8.7524(14)
20.607(3)
1261.8(4)
94.791(7)
100.141(7)
109.862(7)
2
8.569(2)
10.8451(8)
12.1470(10)
1026.82
75.707
11.153(3)
12.206(3)
1065.9(4)
16.9875(10)
1095.87(12)
98.318(3)
91.468(3)
105.343(3)
2
V(Å3)
α
101.257(9)
91.058(9)
110.621(9)
2

89.516
γ
72.029
Z
2
Absorption
coefficient
0.188
0.185
0.164
0.184
mm-1)
(
Dcalc (g/ cm3)
1.357
440
1.362
472
1.291
520
1.351
456
F(000)
Crystal size
(mm)
0.02x0.05x0
.40
0.02x0.03x0
.20
0.07x0.40x0
.70
0.20x0.40x0
.80
θ range for
data
2
.32 to
8.38
2.43 to
25.00
2.50 to
28.34
2.33 to
26.58
2
collection (º)
-
11h11
-14k14
16l16
-9h9
-9k9
-10h10
-11k11
-27l27
-10h10
-13k14
-15l15
Index ranges
-
-20l20
Reflections
collected
4
7651
40160
39732
42764
Independent
reflections
Coverage of
independent
reflections
5146
99.8
3857
100
6282
99.8
4415
99.0
(%)
Data/paramet
ers
5
146 / 274
3857 / 293
6282 / 342
4415 / 284
Max. and
min.
0.929 –
0.996
0.940 –
0.990
0.894 –
0.989
0.867–0.964
transmission
R1 = 0.0457
wR2 =
R1 = 0.0537
wR2 =
R1 = 0.0560
wR2 =
R1 = 0.0455
wR2 =
Final R indices
[
I≥2(I)]
0
.1043
0.1359
0.1475
0.1129
Fig. 8. The crystal packing of compounds 4, 6, 7, and 9
R1 = 0.0851
wR2 =
R1 = 0.0635
wR2 =
R1 = 0.0902
wR2 =
R1 = 0.0722
wR2 =
R indices (all
data)
0.1179
0.1463
0.1664
0.1279
Goodness-of-
fit on F2
1
.008
1.009
1.020
1.012
CCDC No.
1975398
1975395
1975396
1975393
6
| J. Name., 2012, 00, 1-3
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Table 4. The relative energies (ΔE) for the enol-imine and keto-amine forms of 4-9.
View Article Online
DOI: 10.1039/D0NJ03003A
ΔE(kcal/mol)
Gas-phase
THF
DCM
DMF
0.00
DMSO
0.00
Enol-
imine
Keto-
amine
Enol-
imine
Keto-
amine
Enol-
imine
Keto-
amine
Enol-
imine
Keto-
amine
Enol-
imine
Keto-
amine
Enol-
0
6
0
5
0
.00
.23
.00
.24
.00
0.00
0.00
4
4.58
0.00
3.67
0.00
4.34
0.00
3.49
0.00
4.24
0.00
4.41
4.51
0.00
3.59
0.00
4.25
0.00
3.40
0.00
4.16
0.00
4.34
4.20
0.00
3.27
0.00
3.85
0.00
3.04
0.00
3.86
0.00
4.05
4.18
0.00
3.25
0.00
3.82
0.00
3.01
0.00
3.84
0.00
4.03
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
5
6
6.41
0
5
0
5
0
.00
.34
.00
.90
.00
7
8
imine
Keto-
amine
9
5.97
Fig. 9. π—π interaction of the structures 4, 6 and 9
4, 6, 7, and 9 all crystallize in a triclinic lattice with P-1 space
group and all the unit cells contain two molecules (Z=2). All the
structures contain strong intramolecular hydrogen bonding
between phenol and imine moieties with an average distance
of 1.90 Å. A close investigation of the bond distances reveals
that in all the structures enol-imine tautomer are favored over
keto-amine tautomer since C=N double bond distances
referring to imine moieties of 1.28-1.29 Å and C-O sing bond
distances referring to hydroxyl units of 1.34-1.35 Å are in very
Computational Analysis
The optimized structures and stability of 4-9
The compounds (4-9) can be in two possible tautomeric
forms, named as enol-imine and keto-amine, due to the transfer
of hydrogen of the OH proton. The optimized geometries
obtained at B3LYP/631+g(d,p) in the gas phase using the DFT
calculations were illustrated in Fig. 10. The total (E) and relative
energy (ΔE) values in the gas phase and various solvents (THF,
DCM, DMF, and DMSO) were given in Table S34 and Table 4,
respectively. The enol-imine tautomer was more stable than
keto-amine form both of gas phase and in employed solvents
for each compound (Table 4) as consistent with X-ray analysis
of 4, 6, 7, and 9. In addition, the stability of the enol-imine form
of 5-9 was not affected by various substituents at different
positions of phenol moiety as compared with unsubstituted
derivative (4).
1
9,20
close agreement with the literature.
All the geometries
around C=N bonds are trans, in other words, all the structures
are in trans (E) configuration. Structures except 6 contain strong
face-to-face π—π interactions with distances ranging 3.5-3.9 Å
and a shift distances between 1.52-1.75 Å which are shown in
Fig. 9. Coumarin and thiazole moieties are nearly co-planar in
all the structures with a maximum dihedral angle of 9° which is
observed in 6. It should also be noted that the C—C single bond
lengths are in the range of typical C—C single (1.54 Å) and aryl
C—C bonds (1.35 Å), C=N double bond lengths fall also in the
range of 1.28 Å. These observations prove the formation of a
conjugated π system.
This journal is © The Royal Society of Chemistry 20xx
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 8 of 13
Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
View Article Online
DOI: 10.1039/D0NJ03003A
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Fig. 10. The optimized structures of enol-imine and keto-amine tautomers for 4-9.
This journal is © The Royal Society of Chemistry 20xx
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The calculations for sensing mechanism
with their contributions. In case of the addition of cyanide ion
View Article Online
DOI: 10.1039/D0NJ03003A
(
Figs. 11 and S66), the twisting of the phenol moiety with
To gain further insight into the interaction between the respect to the rest of the molecule was found to be about 20-
compounds and F , AcO , CN and H PO
2 4
, the DFT calculations 30°, so the ICT from phenol moiety to thiazole was reduced due
were performed in case of the presence of the anions. The to the interruption of the conjugation. This structural change
optimized structures of the adducts formed via deprotonation observed after the addition of cyanide ion may be a reason for
-
-
-
-
-
-
-
-
interactions with F , AcO , CN and H
2
PO
4
anions and via the the changes in the fluorescence spectra of 4-6 and 8-9.
-
addition of CN were shown in Figs. 11-12 and S65-S66. After the
On the other hand, to explain the driving force in the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-
interaction with anion via deprotonation, the planarity of the nucleophilic addition of CN to the imine bridge, the Mulliken
compounds did not change and there was an insignificant charges of the atoms were also obtained using the same basis
twisting of the phenolic moiety with respect to the rest of the set in DMSO for all compounds. It is clear that the positive
molecule about 2-3°. This indicated that the π-conjugation charges on reactive sites, i.e., C atom in imine bridge, should be
-
between the phenolic and thiazole-coumarin moiety was not enough for the addition reaction of CN . The positive charges on
interrupted. However, the ICT from the phenol moiety to C atom were observed for all studied compounds, except 7, for
thiazole increased after deprotonation due to the increase the example, the charge was found as 0.164e for 4 and -0.186e for
negative charges on oxygen atom (in phenoxide), resulting in a 7 (Figs. 11-12). Moreover, this situation did not change after
new peak in the absorption spectra with a longer wavelength. deprotonation of -OH, i.e., the charge on C25 was still positive
The changes in absorption spectra after the deprotonation for (0.257e) for 4- and was still negative (-0.047e) for 7 .
-
-
4
-9 were seen in Tables S35-S36, including the calculated Accordingly, it is possible to occur the addition of CN for all
absorption maxima, oscillator strength, and related transitions studied compounds, except for 7.
Fig. 11. The optimized structures of 4 and its adducts formed via deprotonation and addition interactions with CN-.
Fig. 12. The optimized structure 7 and its adduct formed via deprotonation interaction with CN-.
Thermal characterization
exhibited good thermal stabilities up to 300 °C which is high
enough for applications in electro-optical device preparation.
To investigate the thermal stability of the compounds,
thermogravimetric analysis (TGA) was used. The
thermogravimetric studies were conducted at 30−600°C under
nitrogen gas at a heating rate of 10°C min . The thermal
stability of the compounds 4-9 is shown in Fig. 13. The
compounds showed zero weight loss up from 0 up to 150°C thus
indicates that there is no water or other organic solvent residue
on the surface of all compounds. The initial decomposition
−1
temperatures (T
d
, 5%) are for 310 (4), 310 (5), 316 (6), 337 (7),
3
00 (8), and 320 °C (9) respectively. Therefore, the compounds
Fig. 13. TGA curves of compounds 4-9
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 10 of 13
ARTICLE
Journal Name
and J = 8.8 Hz, 1H), 6.56 (d, J = 3.4 Hz, 1H), 3.97 (S, 3H) 3.47 (q,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Conclusions
View Article Online
3
DOI: 10.1039/D0NJ03003A
1
J = 7.1 Hz, 4H), 1.25 (t, J = 7.1 Hz, 6H). C-NMR (75 MHz, DMSO-
d
1
4
6
): δ 164.5, 156.0, 151.3, 148.5, 147.4, 141.1, 130.7, 122.8,
In this study, six new cyanide selective candidate
compounds were designed and synthesized. Structural
characterizations of the compounds were done by
spectroscopic and X-ray analysis. All compounds except 7
showed the selective fluorescence turn-on responses to CN-
beside interfering anions in both organic and aqueous solutions.
Chemosensor 7 showed no significant spectral changes towards
anions due to electron donor properties of diethylamino group
at the 4-position of phenyl ring that hindered the addition of
cyanide to imine carbon. The proposed sensing mechanism of
20.1, 119.8, 117.0, 116.2, 113.0, 110.0, 108.4, 96.5, 95.6, 56.4,
+
4.6, 12.8. LC-MS (m/z, ESI+), (M-H) : C24
24 3 4
H N O S: 450.30.
(E)-7-(diethylamino)-3-(2-((2-hydroxy-4-
methoxybenzylidene)amino)thiazol-4-yl)-2H-chromen-2-
one(6):
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
-
1
2
1
93 mg, yield 65 %, m.p. 173 °C, FT-IR (ATR, νmax, cm ): 2962,
1
701, 1616, 1558, 1456. H-NMR (300 MHz, CDCl
3
-d
1
): δ 12.72
(s, 1H), 9.12 (s, 1H), 8.61 (s, 1H), 8.19(s, 1H), 7.43 (d, J = 8.8 Hz,
1
1
1
1
1
H), 7.44 (d, J = 8.2 Hz, 1H), 3.88 (s, 3H) 3.47 (q, J = 7.1 Hz, 4H),
.24 (t, J = 7.1 Hz, 6H). C-NMR (75 MHz, DMSO-d ): δ 170.2,
6
65.6, 164.4, 163.3, 160.2, 156.0, 151.2, 147.2, 141.0, 134.3,
1
chemosensors was explained by H NMR titration study and DFT
1
3
calculations. Interestingly, even though there is gave no
significant spectral changes after anions addition in DMSO
solution of 7, the calculation results showed that there was poor
deprotonation at hydroxyl in the phenyl ring.
Thermogravimetric analysis was conducted to understand the
thermal stability of all the synthesized compounds. In general,
all the dyes showed a good thermal stability up to around 300
30.6, 115.4, 113.3, 113.1, 110.0, 108.4, 101.3, 96.5, 56.1, 44.6,
+
2.8. LC-MS (m/z, ESI+), (M-H) : C24
24 3 4
H N O S: 450.30.
(E)-7-(diethylamino)-3-(2-((4-(diethylamino)-2-
hydroxybenzylidene)amino)thiazol-4-yl)-2H-chromen-2-one(7):
-
1
2
1
96 mg, yield 60 %, m.p. 199 °C, FT-IR (ATR, νmax, cm ): 2970,
o
C
1
707, 1616, 1567, 1469. H-NMR (300 MHz, DMSO-d
6
): δ 12.37
(s, 1H), 9.02 (s, 1H), 8.65 (s, 1H), 7.97 (s, 1H), 7.66 (d, J = 7.2 Hz,
Experimental section
1
1
1
7
H), 7.53 (d, J = 9.0 Hz, 1H), 6.77 (dd, J = 2.2 Hz and J = 8.8 Hz,
H), 6.59 (d, J = 2.1 Hz, 1H), 6.42 (dd, J = 2.2 Hz and J = 9.1 Hz,
H), 6.15 (d, J = 2.2 Hz, 1H), 3.46 (q, J = 7.1 Hz, 8H), 1.15 (t, J =
Materials and equipment
1
3
6
.1 Hz, 12H). C-NMR (75 MHz, DMSO-d ): δ 170.2, 165.6,
General procedure for the synthesis of compounds (4-9)
Compounds were synthesized by mixing of 3-(2-aminothiazol-4- 115.4, 113.3, 113.1, 110.0, 108.4, 101.3, 96.5, 56.1, 44.6, 12.8.
yl)-7-(diethylamino)-coumarin
correspondence salicylaldehyde derivative (1 mmol) in 20 mL
ethanol and three drops of pyrrolidine. The mixture was (E)-3-(2-((5-chloro-2-hydroxybenzylidene)amino)thiazol-4-yl)-
refluxed for 6 h and then cooled, filtered, washed with pure 7-(diethylamino)-2H-chromen-2-one (8):
water, and several times with EtOH and dried in air.
164.4, 163.3, 160.2, 156.0, 151.2, 147.2, 141.0, 134.3, 130.6,
+
(3)
(1
mmol)
and LC-MS (m/z, ESI+), (M-H) : C27
31 4 3
H N O S: 491.50.
-1
351 mg, yield 77 %, m.p. 229 °C, FT-IR (ATR, νmax, cm ): 2955,
1
1
719, 1619, 1559, 1468. H-NMR (300 MHz, CDCl
3
-d
1
): 11.30 (s,
(
E)-7-(diethylamino)-3-(2-((2-
hydroxybenzylidene)amino)thiazol-4-yl)-2H-chromen-2-one
4):
1H), 9.33 (s, 1H), 8.67 (s, 1H), 8.13 (s, 1H), 7.52 (d, J = 2.6 Hz,
1H), 7.43 (d, J = 8.9 Hz, 1H), 7.02 (d, J = 8.9 Hz, 1H), 6.65 (dd, J =
(
2.4 Hz and J = 8.9 Hz, 1H), 6.55 (d, J = 2.2 Hz, 1H), 3.45 (q, J = 7.1
-1
13
3
1
15 mg, yield 71 %, m.p. 175 °C, FT-IR (ATR, νmax, cm ): 2964, Hz, 4H), 1.24 (t, J = 7.1 Hz, 6H). C-NMR (75 MHz, DMSO-d
708, 1615, 1557, 1447. H-NMR (300 MHz, CDCl -d ): δ 12.30 190.2, 170.3, 162.1, 159.3, 156.1, 151.3, 147.5, 141.2, 136.1,
3 1
6
): δ
1
(s, 1H), 9.24(s, 1H), 8.62(s, 1H), 8.24(s, 1H), 7.52 (dd, J = 1.5 Hz 134.7, 130.6, 129.4, 127.8, 121.6, 119.40, 116.6, 110.0, 108.3,
+
and J = 7.2 Hz, 1H), 7.51-7.41 (m, 2H),7.06 (d, J = 8.1 Hz, 1H), 96.5, 54.7, 44.6, 12.8. LC-MS (m/z, ESI+), (M-H) : C23
3 3
H21ClN O S:
6
6
6
1
1
.98 (t, J = 8.3 Hz, 1H), 6.64 (dd, J = 2.5 Hz and J = 8.9 Hz, 1H), 454.40.
.47(d, J = 2.4 Hz, 1H), 3.44 (q, J = 7.1 Hz, 4H), 1.25 (t, J = 7.1 Hz,
H). C-NMR (75 MHz, DMSO-d
56.0, 151.3, 147.4, 141.1, 135.4, 131.7, 130.6, 120.2, 119.9, methylbenzylidene)amino)thiazol-4-yl)-2H-chromen-2-one(9):
17.3, 116.1, 113.0, 110.0, 108.4, 96.5, 95.6, 44.6, 12.8. LC-MS 282 mg, yield 65 %, m.p. 192 °C, FT-IR (ATR, νmax, cm ): 2969,
1
3
6
): δ 170.3, 164.4, 160.7, 160.2, (E)-7-(diethylamino)-3-(2-((2-hydroxy-5-
-1
+
1
(m/z, ESI+), (M-H) : C23
H
22
N O
3 3
S: 420.40.
1705, 1615, 1564, 1484. H-NMR (300 MHz, DMSO-d
6
): δ 11.30
(s, 1H), 9.33 (s, 1H), 8.67 (s, 1H), 8.13 (s, 1H), 7.70 (d, J = 1.8 Hz,
(E)-7-(diethylamino)-3-(2-((2-hydroxy-3-
1H), 7.66 (d, J = 9.0 Hz, 1H), 6.93 (d, J = 8.4 Hz, 1H), 6.77 (dd, J =
2.3 Hz and J = 8.9 Hz, 1H), 6.60 (d, J = 2.2 Hz, 1H), 3.46 (q, J = 7.1
methoxybenzylidene)amino)thiazol-4-yl)-2H-chromen-2-
one(5):
1
3
Hz, 4H), 2.29 (s, 3H), 1.15 (t, J = 7.1 Hz, 6H). C-NMR (75 MHz,
-1
3
1
39 mg, yield 75 %, m.p. 189 °C, FT-IR (ATR, νmax, cm ): 2963, DMSO-d
712, 1616, 1520, 1457. H-NMR (300 MHz, CDCl
6
): δ 192.2, 167.6, 159.15, 156.2, 150.8, 139.6, 137.6,
1
3
-d
1
): δ 12.54 130.1, 129.3, 128.6, 117.6, 109.8, 109.3, 105.4, 96.6, 44.5, 20.2,
+
(s, 1H), 9.28 (s, 1H), 8.65 (s, 1H), 8.27(s, 1H), 7.44 (d, J = 8.8 Hz, 12.8. LC-MS (m/z, ESI+), (M-H) : C24
24 3 3
H N O S: 434.38.
1
H), 7.18 (dd, J = 1.4 Hz and J = 7.8 Hz, 1H), 7.08 (dd, J = 1.8 Hz
and J = 8.0 Hz, 1H), 6.96 (t, J = 7.9 Hz, 1H), 6.66 (dd, J = 2.4 Hz
1
0 | J. Name., 2012, 00, 1-3
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
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S. Campagna, T. Holder and G. Kinsel, Inorg. CheVmiew.,A2rt0ic0le2O,n4lin1e,
Conflicts of interest
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471–2476. (f) Z. Xu, Y. Xiao, X. Qian, J. Cui and D. Cui, Org.
DOI: 10.1039/D0NJ03003A
Lett., 2005, 7, 889–892. (g) F. Y. Wu and Y. B. Jiang, Chem.
Phys. Lett., 2002, 355, 438–444. (h) J. Wang, X. Qian and J. Cui,
J. Org. Chem., 2006, 71, 4308–4311. (i) S. Nishizawa, Y. Kato
and N. Teramae, J. Am. Chem. Soc., 1999, 121, 9463–9464. (j)
H. Yuasa, N. Miyagawa, T. Izumi, M. Nakatani, M. Izumi and H.
Hashimoto, Org. Lett., 2004, 6, 1489–1492. (k) B. Schazmann,
N. Alhashimy and D. Diamond, J. Am. Chem. Soc., 2006, 128,
There are no conflicts to declare.
Acknowledgements
The Scientific and Technological Research Council of Turkey
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607–8614. (l) N. Chandrasekharan and L. A. Kelly, J. Am.
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F. Wang, X. H. Zhang and S. K. Wu, Org. Lett., 2005, 7, 2133–
(TÜBİTAK, project grant 114Z152) for financial support. The
numerical calculations reported in this paper were fully
performed at TUBITAK ULAKBIM, High Performance, and Grid
Computing Center (TRUBA re-sources).
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2003, 5, 2667–2670.
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New Journal of Chemistry
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View Article Online
DOI: 10.1039/D0NJ03003A
We report that synthesis of new Schiff bases containing salicylidene moiety with different
substituents and 7-diethylaminocoumarin-thiazole core. The compounds were
1
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characterization by H/ C NMR spectroscopic and mass spectrometric methods as well as X-
ray crystallography. The compounds except one derivative including diethylamino substituent
on hydroxyphenyl moiety showed highly sensitivity and selectivity to cyanide anions in both
organic and aqueous solution by observed drastic increment at emission intensity.
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New Journal of Chemistry
View Article Online
DOI: 10.1039/D0NJ03003A
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65x87mm (150 x 150 DPI)