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A novel colorimetric and fluorometric probe for the detection of CN with high
selectivity in aqueous media

Guangchen Sun, Wei Chen, Yang Liu, Xin Jin, Zhiyun Zhang, Jianhua Su

PII: S0143-7208(19)32852-9
DOI: https://doi.org/10.1016/j.dyepig.2020.108224
Reference: DYPI 108224

To appear in: Dyes and Pigments

Received Date: 5 December 2019

Revised Date: 7 January 2020
Accepted Date: 17 January 2020

Please cite this article as: Sun G, Chen W, Liu Y, Jin X, Zhang Z, Su J, A novel colorimetric and
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fluorometric probe for the detection of CN with high selectivity in aqueous media, Dyes and Pigments
(2020), doi: https://doi.org/10.1016/j.dyepig.2020.108224.

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Graphical Abstract

A novel colorimetric and fluorometric probe for Leave this area blank for abstract info.
the detection of CN− with high selectivity in
aqueous media
Guangchen Suna, Wei Chena, Yang Liua, Xin Jina, Zhiyun Zhang*,a, and Jianhua Su*,a
a
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science &
Technology, Shanghai 200237, P.R. China.
A novel colorimetric and fluorometric probe for the detection of

CN− with high selectivity in aqueous media

Guangchen Suna, Wei Chena, Yang Liua, Xin Jina, Zhiyun Zhang*,a, and Jianhua Su*,a

a
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science &

Technology, Shanghai 200237, P.R. China.

Corresponding Author. E-mail: zhangzhiyun@ecust.edu.cn; bbsjh@ecust.edu.cn.

Abstract: A novel colorimetric and fluorometric probe L1 for detecting CN− with

high selectivity was constructed and synthesized based on intramolecular charge

transfer (ICT). Remarkably, L1 was found to be exclusively responsive to CN− via

nucleophilic attack of dicyanovinyl group via 1H NMR titration experiment. The

detection system exhibited “turn-on” fluorescence with the addition of cyanide, which

was opposite to previously reported fluorescence quenching probes with the same

sensing process. Moreover, the detection limit of L1 for CN− was determined to be

1.1 µM, lower than the standard (1.9 µM) regulated by the World Health Organization

(WHO). This work demonstrated that L1 could serve as both a colorimetric and a

fluorimetric sensor for cyanide detection in pure water, making it possible for the

applications of cyanide detection in water.

Keywords: Dihydrophenazine; Intramolecular charge transfer; Colorimetric;

Fluorometric; Cyanide
1. Introduction

Anions play a crucial part in the chemical, medical, agricultural and biological

processes [1–2]. Especially for cyanide, its widespread applications cover various

fields, such as nitriles, nylon and acrylic plastic manufacturing, electroplating,

metallurgy, and precious metal extraction [3–4]. However, it is one of the most

harmful and toxic anions to the environment [5–6], which could be accidentally taken

via two main approaches, i.e., skin infiltration and absorption by lung from the

contaminated foods and polluted water [7]. According to the World Health

Organization (WHO), the permissive concentration of cyanide in the drinking water

should be lower than 1.9 µM [8]. Hence, probes for selective and sensitive cyanide

detection are greatly crucial for the mankind daily life.

Lately, a variety of dihydrophenazine analogues have been reported, which were

widely applied in the field of photophysics, photocatalyst and functional fluorescent

materials [9–15]. The triarylamine and hydrophenazine structure provides such strong

electron donating ability that they can be served as an excellent donor. In the

meanwhile, its fluorescent property makes it possible to be applied in the field of

chemosensing. Herein, we intend to develop a novel cyanide probe L1, in utilization

of intramolecular charge transfer (ICT) mechanism (Scheme 1). In this approach,

N,N'-diphenyl-dihydrodibenzo[a,c]phenazine is applied to be a basic framework, in

which the two 9,14-diphenyl moieties are linked with diphenylamine and

dicyanovinyl group at the para- sites, respectively, forming a typial D-π-A structure

with intense ICT effect. Furthermore, with the dicyanovinyl group as a reactive site
[16], it can act as both colorimetric and fluorimetric sensor for detecting cyanide in

water in the presence of cetyltrimethylammonium bromide (CTAB) [17].

Fluorescence intensity of the sensor system could show increasing trendency upon the

nucleophilic attack reaction, which is opposite to the previously reported fluorescence

quenching probes with the same sensing process [18–20]. Fortunately,

dihydrophenazine-based colorimetric and fluorimetric sensor L1 for CN− was

obtained with good selectivity in the aqueous environment.

2. Experimental Section

2.1 Materials

All reactants were acquired commercially, and applied as received without

further purification. N,N-dimethylformamide (DMF) and ortho-xylene were dried

through 4 Å molecular sieves. Deionized water was applied and acquired from a

Millipore Milli-Q plus system. Cyanide anion was in the form of tetrabutylammonium

salts, selectivity detection samples of other anions were used from the corresponding

sodium salts.

2.2 Instruments and methods

1 13
H NMR and C NMR experiments were carried out on Brucker AM-400

spectrometers, in which tetramethylsilane (TMS) in CDCl3 or DMSO-d6 was applied

to be the internal standard. HRMS were performed on Waters LCT Premier XE

spectrometer. Single-crystal was analysed via X-ray diffraction. UV-visible

absorption experiments were carried out on Varian Cray 500 spectrophotometer.

Fluorescence experiments were carried out on Varian Cray Eclipse. The geometry of
compound L1 at ground state was optimized through time-dependent density function

theory (TD-DFT) with B3LYP hybrid function and 6-31+G(d,p) basis set. The

electronic wavefunction analysis was conducted by Multiwfn program [21].

2.3 Synthesis

9-(4-bromophenyl)-14-phenyl-9,14-dihydrodibenzo[a,c]phenazine (2). The

mixture of compound 1 (7.2 g, 20.0 mmol), 1-bromo-4-iodobenzene (5.6 g, 19.8

mmol), K2CO3 (3.4 g, 24.3 mmol), Copper(II) trifluoromethanesulfonate (1.8 g, 5.0

mmol) and sym-trichlorobenzene (20.0 g) were put into a flask. The mixture kept

stirring for 8 h in the dry air. Afterwards, the sym-trichlorobenzene was removed in a

vacuum. The residue was dispersed in 60 mL DCM and then filtered. The filtrate was

gathered. The crude product was purified through column chromatography on silica

gel (PE: EA = 50: 1) to afford light yellow solid (yield: 5.0 g, 48.7 %). 1H NMR

(DMSO-d6, 400 MHz, TMS), δ: 8.95 (d, J = 8.3 Hz, 2H), 7.97–7.90 (m, 4H), 7.74–

7.62 (m, 4H), 7.47–7.43 (m, 2H), 7.22 (d, J = 9.1 Hz, 2H), 7.11–7.07 (m, 2H), 7.01

13
(d, J = 7.8 Hz, 2H), 6.89–6.83 (m, 3H). C NMR (CDCl3, 100 MHz) δ: 147.35,

146.69, 144.95, 144.22, 138.43, 137.50, 131.50, 129.94, 129.84, 129.29, 129.06,

128.84, 127.43, 127.10, 127.03, 126.70, 126.64, 125.73, 125.41, 124.65, 124.27,

123.11, 123.02, 121.25, 117.68, 116.71, 113.13. HRMS ESI (m/z) [M+H]+: calcd. for

C32H22N2Br, 513.0966, found 513.0968.

4,4'-(dibenzo[a,c]phenazine-9,14-diyl)dibenzaldehyde (3). In a dry three-necked

flask, DMF (12.8 mL, 80.0 mmol) was first added. The flask was placed into an

ice-water bath. Then phosphorus oxychloride (6.3 mL, 39.8 mmol) was added
dropwise under argon. The mixture kept stirring for 1 h. Afterwards, compound 2 (4.2

g, 8.2 mmol) in 80 mL DMF was added dropwise. The solution was kept stirring for

10 h at 80 °C. Then, the mixture was cooled down and poured into ice water. The pH

value was adjusted to 7.0. The mixture was then filtered. The residue was gathered

and purified through column chromatography on silica gel (PE/DCM = 10:1),

obtaining a kelly solid (yield: 2.6 g, 58.7%). 1H NMR (DMSO-d6, 400 MHz, TMS),

δ: 9.72 (s, 1H), 8.78 (d, J = 10.2 Hz, 2H), 8.04 (t, J = 6.8 Hz, 2H), 7.79–7.76 (m, 2H),

7.74–7.68 (m, 2H), 7.63–7.58 (m, 2H), 7.56–7.53 (m, 2H), 7.45–7.40 (m, 2H), 7.09

13
(d, J = 12.2 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 6.82 (d, J = 15.2 Hz, 2H). C NMR

(CDCl3, 100 MHz), δ: 190.64, 151.90, 145.94, 144.74, 143.32, 138.49, 137.22,

131.75, 131.33, 127.88, 127.74, 127.45, 127.34, 127.29, 126.52, 125.92, 124.19,

123.36, 123.28, 117.83, 114.37, 113.77.

4-(14-(4-(diphenylamino)phenyl)dibenzo[a,c]phenazine-9(14H)-yl)benzaldehyde

(4). Compound 3 (2.5 g, 4.6 mmol), diphenylamine (0.78 g, 4.6 mmol) and potassium

tert-butoxide (0.76 g, 5.5 mmol) was dissolved in dry ortho-xylene (40 mL).

Tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (0.21 g, 0.23 mmol),

tri-tert-butylphosphonium tetrafluoroborate (P(t-Bu)3HBF4) (0.13 g, 0.46 mmol) were

then added. The mixture kept refluxing with vigorous stirring for 15 h under argon.

After cooling down, the precipitation was removed through filteration. The solvent

was evaporated in vacuum. The residue was purified through column chromatography

on silica gel (PE/DCM = 10:1), obtaining Kelly solid (yield: 1.5 g, 51%). 1H NMR

(DMSO-d6, 400 MHz, TMS), δ: 9.76 (s, 1H), 8.77 (d, J = 8.3 Hz, 2H), 8.24 (d, J = 7.2
Hz, 1H), 8.07 (d, J = 8.2 Hz, 1H), 7.78–7.73 (m, 2H), 7.72–7.68 (m, 2H), 7.64–7.59

(m, 2H), 7.55 (d, J = 8.9 Hz, 2H), 7.41–7.31 (m, 2H), 7.15–7.08 (m, 2H), 6.94 (d, J =

8.9 Hz, 2H), 6.89 (t, J = 7.3 Hz, 2H), 6.84–6.81 (m, 6H), 6.72 (d, J = 9.0 Hz, 2H). 13C

NMR (DMSO-d6, 100 MHz), δ: 190.60, 152.79, 147.70, 145.95, 143.43, 143.15,

142.05, 139.72, 136.72, 131.15, 129.00, 127.20, 127.10, 125.50, 125.47, 123.30,

123.24, 123.15, 122.16, 119.07, 114.64. HRMS ESI (m/z) [M+H]+: calcd. for

C45H31N3O, 629.2467, found 629.2532.

2-4-(14-(4-(diphenylamino)phenyl)dibenzo[a,c]phenazine-9(14H)-yl)benzylidene

)malononitrile (L1). The mixture of 4 (1.0 g, 1.5 mmol), ammonium acetate (0.15 g,

1.8 mmol) and excess malononitrile was added to 30 mL acetic acid. The solution was

then refluxed under argon for 12 h. After cooling down, the mixture was poured into

ice water. Afterwards, the mixture was filtered and purified through silica gel column

chromatography (PE/DCM = 10:1). An orange solid was obtained (yield: 0.7 g, 63%).

1
H NMR (DMSO-d6, 400 MHz, TMS), δ: 8.99 (d, J = 8.4 Hz, 2H), 8.24 (s, 1H), 8.10

(d, J = 8.5 Hz, 1H), 7.99–7.95 (m, 3H), 7.79–7.67 (m, 6H), 7.50–7.48 (m, 2H), 7.19

(t, J = 7.9 Hz, 4H), 7.01 (d, J = 9.0 Hz, 4H), 6.94 (t, J = 7.4 Hz, 2H), 6.79 (d, J = 7.7

Hz, 4H), 6.74 (d, J = 9.0 Hz, 2H). 13

C NMR (DMSO-d6, 100 MHz), δ: 152.83,

147.63, 145.66, 142.69, 141.76, 139.40, 132.84, 129.10, 127.56, 127.29, 127.25,

127.20, 126.98, 126.93, 126.58, 125.14, 123.63, 123.55, 123.43, 122.45, 120.08,

114.95, 114.92, 113.84, 76.18. HRMS ESI (m/z) [M+H]+: calcd. for C48H31N5,

677.2579, found 677.2597.

3. Results and Discussion

3.1 Synthesis

The complete synthetic route of L1 was exhibited in Scheme 1. The raw

material, compound 1, was obtained according to the reported literatures [22]. The

reaction of 1 with 1-bromo-4-iodobenzene had been conducted to afford compound 2

through Cu-catalyzed C-H amination and Ullmann N-arylation [23]. Compound 3 was

then synthesized by the Vilsmeier-Haack reaction of compound 2 with synthetic

Vilsmeier reagent, which subsequently reacted with diphenylamine to afford

compound 4 on the basis of Buchwald-Hartwing Coupling reaction. The target

compound L1 was obtained by the reaction of compound 4 with excess malononitrile.

All the compounds were detailed characterized through 1H NMR, 13

C NMR, HRMS

(see the Supporting Information). Meanwhile, the single-crystal of compound 3 was

prepared via slow evaporation from mixed solvents (dichloromethane/ethanol), and

the structure as well as X-ray diffraction intensity data were shown in Fig. 1 and

Table S1, respectively.

Scheme 1 Synthesis route of L1. Reagents and conditions: i) 1-bromo-4-iodobenzene,

sym-trichlorobenzene, Cu(CF3SO3)2, K2CO3, reflux; ii) DMF, POCl3; iii) diphenylamine, t-BuOK,

Pd2(dba)3, P(t-Bu)3HBF4, ortho-xylene, reflux; iv) CNCH2CN, CH3COONH4, CH3COOH, reflux.

 Fig. 1 The single crystal X-ray structure of 3.

3.2 Computational approach

For further insight into the excited state of compound L1, TD-DFT were

conducted. The calculated lowest excited state (S1) of L1 corresponded to

HOMO→LUMO transition were shown in Fig. 2. The electron density for HOMO of

L1 was delocalized over the central moiety, including the triphenylamine moiety, and

partially extended to the adjacent N atom in the dihydrophenazine part. In sharp

contrast, the electron density for LUMO of L1 was mainly located at

benzylidenemalononitrile. Due to the significantly seperation of the HO and LU

molecular orbitals, the electron can transfer from triphenylamine part (donor) to

benzylidenemalononitrile part (acceptor) upon excitation, resulting in a remarkable

ICT effect and fluorescence quenching in aqueous solution.

Fig. 2 The HOMO and LUMO of compound L1.

3.3 Spectra titration

 We firstly explored the concentration dependent experiments of L1 through the

absorption and fluorescence spectra with the addition of CN−. The sensing system was

prepared by mixing compound L1 (50 µL, 2.0 mM) in DMSO and CTAB in water

(4.95 mL, 1.0 mM) [24].

Fig. 3 Absorption (a) and fluorescence (b) spectra of L1 (20 µM) in DMSO/H2O (1:99, v/v, containing

1 mM CTAB) upon addition of 0−9.0 equiv. of aqueous CN−. λex = 310 nm. Inset: the corresponding
color (a) and emission (b) changes of L1 upon addition cyanide. (c) Plot of emission intensity versus

cyanide concentration (from 0 to 40 µM, λex = 310 nm, λem = 496 nm, R2 = 0.9730, k = 0.43 µM-1, σ =

0.16. The standard deviation (σ) was acquired by 10 curves of the emission spectra at the starting

detection point. The detection limit was determined to be 1.12 µM according to the formula (3σ/|k|).

As shown in Fig. 3a, probe L1 was light yellow, exhibiting the absorption peaks

centered at 300 nm and 420 nm, respectively. With gradual titration of 9.0 equivalent

of CN−, absorption peak intensity at 420 nm decreased and eventually disappeared,

which led the solution to become colorless. This change suggested that the large

π−conjugation of L1 was broken since the nucleophilic reaction broken the double

bond of vinyl. The result demonstrated clearly that L1 can serve as an ideal candidate

for cyanide detection in water through naked eyes.

Moreover, the fluorescence spectra titration as well endorsed its application in

the quantitative analysis of cyanide. As shown in Fig. 3b, the free L1 exhibited

severely quenching fluorescence. With the addition of CN−, the emission at 496 nm

kept increasing. Ultimately, the emission intensity at 496 nm became saturated when

the amount of CN− reached 9.0 equivalent. Meanwhile, the emission intensity at 496

nm and the concentration of cyanide at low region exhibited good linear relationship

(Fig. 3c). The detection limit (DL) was calculated according to the standard formula

3σ/|k|, in which σ is the standard deviation of the fluorescence intensity and k is the

slope of the calibration curve [25–26]. The DL was determined to be 1.12 µM, lower

than the standard (1.9 µM) set by WHO. These results proved that probe L1 owned a
high sensitivity toward cyanide in nearly pure water, which could act as both

colorimetric and fluorimetric sensor of cyanide in aqueous solution.

3.4 Optical response to various ions

Sensitivity of probe L1 for cyanide was validated as above. Then we performed

the research on the selectivity of L1. Probe L1 (20 µM) was treated with different

anions species including 9.0 equivalent of CN−, and 50.0 equivalent of F−, Cl−, Br−, I−,

NO3−, AcO−, HSO4−, H2PO4− in DMSO/water solution (1/99, v/v, containing 1 mM

CTAB). The responses of L1 to various anions were shown in Fig. 4. Upon addition

of 9.0 equiv. of CN− into the solution of L1, the absorption band at 420 nm decreased

sharply which led to distinct color change from yellow to colorless, which could be

observed by naked eyes (Fig. 4a, inset). The emission spectra of corresponding

samples were then measured by fluorescence spectrophotometer. In Fig. 4b, an

obvious increase of the emission intensity at 496 nm could be observed only with the

addition of CN−. However, the probe with other anions exhibited little response.

Corresponding photos of the fluorescence color changes were taken under 365 nm UV

illumination (Fig. 4b, inset). These results demonstrated that L1 owned high

selectivity toward cyanide in nearly pure water.

Moreover, the competition experiments were performed to prove the high

competitiveness of probe L1 to cyanide in the face of higher concentration of

interfering anions. As shown in Fig. 5, the fluorescence of the probe system was

nearly invariable upon addition of 50.0 equivalent of other anions, while obviously

increased emission as a sharp contrast upon subsequent addition of 9.0 equivalent of

cyanide was observed. The emission intensity at 496 nm versus response time was

also conducted in order to explore its sensitivity. The response time was determined to

be less than 4 min as shown in Fig. S12. All these experiments revealed that L1 was

an efficient fluorescence “turn-on” probe with excellent selectivity for detecting

cyanide in aqueous solution, which was ascribed to the specific nucleophilic attack of

cyanide toward the dicyanovinyl, indicating its enormous potential in the cyanide

detection applications.

Fig. 4 Absorption spectra (a) and emission spectra (b) of L1 (20 µM) in DMSO/H2O solution (1:99,

v/v, containing 1 mM CTAB) upon addition of 9.0 equiv. of CN− and 50.0 equiv. of various anions (F−,

Cl−, Br−, I−, NO3−, AcO−, HSO4−, and H2PO4−). Inset: the corresponding color (a) and emission (b)

changes of L1 upon addition of various anions.

Fig. 5 Emission spectra response of L1 (20 µM in DMSO/H2O (1:99, v/v, containing 1 mM CTAB) in

the presence of various anions (50.0 equiv.) and CN− (9.0 equiv.); (λex = 310 nm, λem = 496 nm).

3.5 1H NMR titration experiments and detection mechanism

As a reactive unit, the dicyanovinyl group has been generally adopted to design

cyanide sensors based on chemical reaction. Compound L1 thus may be qualified for

the cyanide detection in aqueous media with dicyanovinyl group as the recognition

site [27–29]. 1H NMR titration spectra was performed to take deep insight into the

reaction processes of L1 with CN−. Fig. 6 presented the 1H NMR titration spectra of

L1 in DMSO-d6 with different equivalent of CN−. The vinylic proton (Ha) at 8.24

ppm decreased with the addition of cyanide and disappeared eventually when

reaching 1.5 equivalent. Simutaneously, a new signal was observed at 4.40 ppm (Hb).

It was induced by the broken conjugation of the vinyl group, which was caused by

nucleophilic addition of the cyanide toward dicyanovinyl group (Scheme 2).

 Fig. 6 1H NMR titration spectra of L1 in DMSO-d6 with addition of CN−.

Scheme 2 The nucleophilic reaction of cyanide toward L1.

Based on the spectra and 1H NMR titration experiments, the reasonable

interpretation of fluorescence “turn-on” mechanism could be provided. The intense

ICT effect of compound L1 in the DMSO/H2O (1:99, v/v) solution with high polarity

quenched its fluorescence [30], resulting in rather weak emission in absence of

cyanide. However, with the addition of cyanide, the π-conjugation was interrupted

and a [CN–L1]− adduct was subsequently formed because of nucleophilic attack of

cyanide toward the dicyanovinyl (Scheme 2). Therefore, the intramolecular charge

transfer system was broken, resulting in the intrinsic emission of the

N,N'-diphenyl-dihydrophenazine substituted by diphenylamine group at the para-

position [31].

4. Conclusion

In summary, probe L1 with N,N′-disubstituted-dihydrophenazine framework and

dicyanovinyl group have been designed and synthesized for quantitative analysis of

cyanide in aqueous media based on ICT mechanism, which is able to function as a

“turn-on” fluorescent chemosensor for CN− with high selectivity in nearly pure water.

After adding 9.0 equiv. of cyanide, the absorption peak at 420 nm faded away and the

emission band centered at 496 nm have remarkablely increased, which result in a

colorless detection system with intense green fluorescence. A colorimetric and

fluorimetric response to cyanide is thus achieved via the nucleophilic attack to the

dicyanovinyl group, which is quite superior to previous fluorescence quenching

probes of cyanide. Moreover, the DL of L1 is determined to be 1.1 µM by the

fluorescence spectroscopy method, which is lower than the standard (1.9 µM)

regulated by WHO, enabling it an ideal water sensor for potential applications.

Moreover, this work not only provides an example of colorimetric and fluorimetric

sensor to quantitative analysis of cyanide in aqueous media, the molecular design

concept can also promote future research in the field.

ACKNOWLEDGEMENTS

We thank the financial support from the NSFC/China (21788102, 21905090,

21790361), Shanghai Municipal Science and Technology Major Project (Grant

No.2018SHZDZX03), the Programme of Introducing Talents of Discipline to

Universities (B16017), the Program for Professor of Special Appointment (Eastern

Scholar) at Shanghai Institutions of Higher Learning, and Natural Science Foundation

of Shanghai (19ZR1412200).

ASSOCIATED CONTENT

Electronic Supporting Information (ESI) Available: The characterization (NMR and

HRMS), single crystal analysis data, and response time data were included.

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 Authors Individual contributions

Methodology, Software, Formal analysis, Investigation, Data Curation,

Guangchen Sun
Writing−Original Draft, Visualization

Wei Chen Conceptualization, Methodology, Formal analysis

Yang Liu Validation, Investigation

Xin Jin Software

Resources, Writing−Review & Editing, Project administration, Funding

Zhiyun Zhang
acquisition

Jianhua Su Project administration, Supervision

Highlights

A novel fluorescence “turn-on” probe for detecting cyanide was designed and

synthesized based on intramolecular charge transfer (ICT).

The probe can act as a colorimetric and a fluorimetric sensor in nearly pure water

with the assistance of CTAB.

The probe possessed high selectivity for the detection of cyanide.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: