Dyes and Pigments 215 (2023) 111243

Contents lists available at ScienceDirect

Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Cyanide detecting porphyrin fluorescent sensors: Effects of

electron-donating/withdrawing substituents
Jiyoung Hwang 1, T. Sheshashena Reddy 1, Hyungkyu Moon , Hae Dong Lee , Myung-Seok Choi *
Department of Materials Chemistry and Engineering, Konkuk University, 120 Neungdong-ro, Gwangjin-gu, Seoul, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: The detection of cyanide (CN− ) and other dangerous chemicals is critical in many practical scenarios. In this
Dicyanovinylporphyrin study, dicyanovinylporphyrins (DCVPs) 2a to 2d with electron-donating or electron-withdrawing substituents as
Cyanide ion fluorescent sensors for CN− detection were synthesized through Lindsay’s condensation reaction. The 2a to 2d
Fluorescent sensor
absorption, fluorescence, and fluorescence lifetimes of the DCVPs were investigated in THF. To probe the
Electron-donating/withdrawing
reactivity of DCVPs to CN− , the electron density of β-carbon in their dicyanovinyl groups was controlled by
introducing electron-donating or electron-withdrawing groups. The anion (Cl− , Br− , I− , ClO−4 , HSO−4 , NO−3 , and
CN− ) sensing abilities of DCVPs 2a to 2d were investigated through fluorescence spectroscopy in THF. The
DCVPs exhibited selective reduction in fluorescence intensity upon the addition of CN− ions. DCVP 2d also
exhibited strong detection capabilities for CN− ions. Specifically detection limit for CN− was found to be 3.14 ×
10− 8 M in THF.

1. Introduction molecules in biological systems, optoelectronics, and sensors [3,33–35].

In biology, porphyrins are responsible for various essential processes
Recently, based on the understanding that anions play a critical role that sustain life, including photosynthesis, electron transport in redox
both chemically and biologically, supercritical chemistry has attracted processes, oxygen transport and storage, and biocatalysis [33,34]. In
significant interest for developing anion recognition systems [1–7]. photonics, porphyrins are used for photothermal therapy, photodynamic
Among various anions, cyanide (CN− ) is a highly toxic substance. When therapy, near-infrared fluorescence imaging, magnetic resonance im­
it enters the human body through breathing, drinking, eating, or skin aging, dye-sensitized solar cells, nonlinear optics, and catalysis [36–39].
contact, it disables the action of cytochromes, which perform various As shown in Fig. 6, Xie et al. and Sankar et al. reported DCV-based
functions in vivo [5,6,8] It also binds to the heme in red blood cells, porphyrin CN− sensors (Fig. 6). Xie et al. reported sensors using DCV
leading to hypoxia and death [5,6,8] CN− is highly poisonous at appended at the meso-positions of porphyrins and investigated their
extremely low concentrations of 0.01 (mg/L), making it significantly CN− -sensing abilities using fluorescence spectroscopy. The DCV group
more dangerous than most other hazardous substances, including lead appended at the meso-position of porphyrin was initially
(0.05 (mg/L)) and arsenic (0.05 (mg/L)) according to water quality non-fluorescent. However, upon the nucleophilic addition of CN− , the
management standards [8]. A large proportion of the CN− in the envi­ porphyrin exhibited fluorescence behavior [40]. Sankar et al. reported
ronment is generated by industrial processes such as mining and plating the attachment of DCV groups at the β-positions of porphyrins and
[6]. Various systems capable of detecting CN− ions have been studied. investigated their CN− ion-sensing ability using ultraviolet–visible
Among such systems, chemical sensor systems provide excellent selec­ (UV–vis) absorption spectroscopy [41–43]. Thus far, there have been no
tivity, low cost, ease of detection, and biological applicability. reports on the effects of electron-donating and electron-withdrawing
Several research groups have reported the synthesis of CN− sensors groups in dicyanovinylporphyrins (DCVPs) on the sensing of CN− .
using various fluorescent probes, including nucleophilic addition-based This paper reports the design and synthesis of DCVPs, their photo­
probes containing dicyanovinyl (DCV), cyanine, triarylborane, and physical properties, and their sensing ability for CN− .
carbonyl groups [9–32] Porphyrins are fascinating and important

* Corresponding author.
E-mail address: [email protected] (M.-S. Choi).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.dyepig.2023.111243
Received 10 January 2023; Received in revised form 1 March 2023; Accepted 14 March 2023
Available online 18 March 2023
0143-7208/© 2023 Elsevier Ltd. All rights reserved.
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

2. Experiments emalononitrile)-21H,23H-porphyrin (2a): Yield 14% (0.17 g). 1H

NMR (CDCl3, 600 MHz) δ 10.407 (s, 1H, vinyl− H), 10.330 (s, 1H,
2.1. General methods meso− H), 10.326 (s, 1H, meso− H), 9.429− 9.402 (m, 4H, β− H), 9.237
(dd, 2H, J1− 2 = 0.505 Hz, J1− 3 = 4.547 Hz, β− H), 9.011− 8.99 (m, 2H,
All chemicals were purchased from commercial sources and used β− H), 8.456− 8.425 (m, 2H, Ar–H), 8.322 (d, 2H, J = 8.322 Hz, Ar–H),
without further purification. 1H nuclear magnetic resonance (NMR) 8.138− 8.099 (m, 2H, Ar–H), 7.511 (d, 2H, J = 8.33 Hz, Ar–H),
spectra were recorded using a 600 MHz Bruker Ultrashield and (Avan­ 7.447− 7.437 (m, 8H, Ar–H), 7.190− 7.159 (m, 2H, Ar–H), − 3.066 (2H,
ceIII) NanoBay spectrometer. All spectra were recorded at 298 K. The 1H s, –NH). 13C NMR (CDCl3, 125 MHz) δ 159.73, 147.87, 146.33, 145.45,
NMR data are reported as follows: s, singlet; d, doublet; t, triplet; m, 145.16, 136.09, 135.95, 135.58, 134.71, 132.41, 132.19, 131.85,
multiplet; with coupling constants J given in Hz. The chemical shifts in 131.58, 131.47, 130.43, 130.2, 130.15, 129.66, 129.39, 128.37, 125.14,
the 1H NMR spectra are reported in parts per million (ppm) with tet­ 123.56, 123.52, 121.59, 105.85, 105.67, 83.24. MALDI-TOF-MS: m/z
ramethylsilane (0 ppm) as the standard. Mass spectroscopy was per­ calculated as 706.26 [M+H]+ and measured as 706.28 [M+H]+.
formed using an ABSCIEX TOF/TOF™ 5800 System (SHIMADZU- Synthesis of 5-(hexyl)-15-(4-benzylidenemalononitrile)-21H,2
Biotech AXIMA-Confidence). Thin-layer chromatography analyses were 3H-porphyrin (2b): Yield 18% (0.17 g). 1H NMR (CDCl3, 500 MHz) δ
performed using silica gel 60 F254 plates. UV–vis absorption spectra were 10.389 (s, 0.32H, vinyl− H), 8.045 (s, 0.64H, vinyl− H), 10.237 (s, 1H,
recorded in various solvents using a Jasco V-670 UV–vis spectropho­ meso H), 10.232 (s, 1H, meso H), 9.613 (d, 2H, J = 5 Hz, β− H), 9.426 (d,
tometer. Emission spectra were collected using a Hitachi F-7000 fluo­ 2H, J = 4.5 Hz, β− H), 9.375− 9.354 (m, 2H, β− H), 8.954− 8.928 (m, 2H,
rescence spectrophotometer. The excitation and emission slits were 5 β− H), 8.396− 8.365 (m, 2H, Ar–H), 8.301− 8.257 (m, 2H, Ar–H), 5.031
nm in length for the emission measurements. The fluorescence lifetimes (t, 2H, J = 8 Hz, –CH2), 2.599− 2.537 (m, 2H, –CH2), 1.832− 1.797 (m,
were recorded using a Fliorolog-QM instrument (HORIBA). All mea­ 2H, –CH2), 1.531− 1.501 (m, 2H, –CH2), 1.426− 1.396 (m, 2H, –CH2),
surements were performed at 298 K. Column chromatography was 0.937 (t, 3H, J = 7.5 Hz, –CH2), − 2.994 (s, 2H, –NH). 13C NMR (CDCl3,
performed using Merck silica gel (230–400 mesh). 125 MHz) δ 159.67, 148.47, 147.56, 146.5, 144.82, 136.03, 135.53,
Synthesis of 2¡(4¡formylbenzylidene)malononitrile (1): 4− 132.41, 132.17, 132.08, 130.16, 129.87, 129.36,128.47, 128.34,
(Dimethoxymethyl) benzaldehyde (5 g, 24 mmol) and malononitrile 120.95, 120.58, 115.36, 113.99, 112.93, 105.39, 105.2, 83.2, 38.92,
(2.8 g, 42 mmol) were dissolved in ethanol (35 ml) with a catalytic 34.98, 31.99, 30.371, 22.81, 14.20. MALDI-TOF-MS: m/z calculated as
amount of piperidine. The reaction mixture was refluxed for 30 min and 546.2532 [M+H]+ and measured as 547.20 [M+H]+.
the solvent was removed under reduced pressure. The crude product was Synthesis of 5-phenyl-15-(4-benzylidenemalononitrile)-21H,23
purified through column chromatography on silica gel using ethyl ace­ H-porphyrin (2c): Yield 13% (0.12 g). 1H NMR (CDCl3, 500 MHz) δ
tate/hexane (1:4, v/v) as an eluent. The purified product (2.8 g, 11 10.42 (s, 1H, vinyl− H), 10.339 (s, 2H, meso− H), 9.428− 9.398 (m, 4H,
mmol) was dissolved in 16 ml of chloroform and dropped into 24 ml of β− H), 9.095 (d, 2H, J = 4.295 Hz, β− H), 9.020 (d, 2H, J = 4.547 Hz,
trifluoroacetic acid-water (1:1, v/v) at 0 ◦ C. After 2 h of stirring at 0 ◦ C, β− H), 8.463 (d, 2H, J = 7.579 Hz, Ar–H), 8.336 (d, 2H, J = 7.579 Hz,
300 ml of water was added, followed by extraction with chloroform Ar–H), 8.285− 8.246 (m, 2H, Ar–H), 7.824− 7.799 (m, 3H, Ar–H),
(200 mL) in triplicate. The organic layer was separated and washed with − 3.103 (2H, s, –NH). MALDI-TOF-MS m/z calculated as 539.19 [M +
a saturated brine solution. After drying over sodium sulfate, the solution H]+ and measured as 539.11 [M+H]+.
was concentrated under vacuum, resulting in product. Yield 42% (2.1 g). Synthesis of 5-(4-(trifluoromethyl)-phenyl)-15-(4-benzylidene­
1
H NMR (CDCl3, 500 MHz) δ 10.118 (s, 1H), 8.08− 8.037 (m, 4H, aro­ malononitrile)-21H,23H-porphyrin (2d): Yield 12% (0.12 g). 1H
matic), 7.867 (1H, s). 13C NMR (CDCl3, 100 MHz) δ 190.88, 158.41, NMR (CDCl3, 500 MHz) δ 10.435 (s, 1H, vinyl− H), 10.382 (s, 2H,
139.69, 135.63, 131.24, 130.55, 113.24, 112.17, 86.34. meso− H), 9.455− 9.444 (m, 4H, β− H), 9.044 (t, 4H, J = 4.5 Hz, β− H),
General procedure for the synthesis of DCVPs(2a¡2d): Dipyrro­ 8.475 (d, 2H, J = 8 Hz, Ar–H), 8.414 (d, 2H, J = 8 Hz, Ar–H), 8.356 (d,
methane (0.5 g, 3.42 mmol), 2− (4− formylbenzylidene), malononitrile 2H, J = 8 Hz, Ar–H), 8.096 (d, 2H, J = 7.5 Hz, Ar–H), − 3.138 (s, 2H,
(0.31 g, 1.71 mmol), and respective aldehyde (1.71 mmol) were dis­ –NH). MALDI-TOF-MS: m/z calculated as 607.17 [M+H]+ and measured
solved in 500 mL of chloroform and degassed in a stream of N2 for 10 as 607.13 [M+H]+.
min. Trifluoroacetic acid (0.16 mL, 2.05 mmol) was added to this so­
lution and the reaction mixture was stirred under N2 at room tempera­ 3. Results and discussion
ture for 2 h. Chloranil (1.05 g, 4.28 mol) was added to the reaction
mixture and stirred for another 1 h at room temperature. The reaction 3.1. Design and synthesis of DCV-porphyrins
mixture was filtered and concentrated under vacuum following
neutralization with triethylamine (1 mL). The residue was purified Various DCVP molecules, containing strong electron-donating (2a),
through silica gel column chromatography with chloroform as an eluent weak electron-donating (2b, 2c) and strong electron-withdrawing sub­
to derive a pure product. stituents (2d), were designed to modulate the charge density of the
Synthesis of 5-(4-(diphenylamino)phenyl)-15-(4-benzyliden β-carbon in the DCV groups. In DCVP 2a, as a result of intramolecular

Fig. 6. The cyanide ion binding mechanism for the 2b (top) and 1H–NMR spectrum of 2b and 2b þ TBACN in CDCl3 (bottom).

2
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

charge transfer (ICT) from the triphenylamine electron donor unit to the absorption spectrum contains a broadened absorption peak compared to
DCV unit, the β-carbon in the DCV group may exhibit a very low elec­ those of DCVPs 2b to 2d as a result of strong charge transfer between the
trophilic nature. The β-carbon in the DCV group in DCVPs 2b and 2c triphenylamine electron-donor unit and DCV electron acceptor unit.
may exhibit a moderately electrophilic nature based on weak ICT from This finding is supported by DFT calculations.
the phenyl and hexyl units to the DCV unit. However, in DCVP 2d, the To investigate the effects of substituents on porphyrin’s intrinsic
β-carbon in the DCV group may exhibit a relatively high electrophilic fluorescence, the fluorescence lifetimes of DCVPs 2a to 2d were
nature based on the absence of ICT by electron-withdrawing tri­ measured in THF at 25 ◦ C. Fig. S13 presents the time-resolved fluores­
fluoromethyl group. cence decay monitored at λ = 640 nm for DCVPs 2a to 2d upon exci­
To gain a deeper understanding of the design of DCVPs, we per­ tation at λ = 405 nm in THF at 25 ◦ C. The fluorescence lifetimes were
formed density functional theory (DFT) calculations for DCVPs 2a to 2d calculated as 8.66 (2a), 9.56 (2b), 9.67 (2c) and 9.87 ns (2d) (Table S1).
using the Gaussian 09 program. The frontier molecular orbitals (HOMO These results indicate that electron electron-donating/withdrawing
and LUMO) of DCVPs 2a to 2d are presented in Chart 1. In DCVP 2a substituents had little effect on the excited state of the porphyrin bodies.
having a strong electron-donating group, the highest occupied molecu­ To investigate the electrophilic addition reactivity at the β-carbon in
lar orbital (HOMO) is located on the strong electron-donating triphe­ DCVPs 2a to 2d, we conducted a CN− sensing experiment with other
nylamine and porphyrin units, and the lowest occupied molecular anions such as Cl− , Br− , I− , ClO−4 , HSO−4 and NO−3 using fluorescence
orbital (LUMO) is located in the DCV group (Chart 1). In the DCVP 2d spectroscopy in THF (Fig. 2). DCVPs 2a to 2d exhibited selective fluo­
having the strong electron-withdrawing, the HOMO is mainly located on rescence turn-off sensing ability for CN− and were unresponsive to other
the porphyrin unit, and the LUMO is mainly located in the DCV group. anions. Furthermore, the fluorescence quenching of DCVPs 2a to 2d in
DCVP 2b and 2c having the weak electron-donating substituent shows the presence of CN− were observed to be 30%, 39%, 41%, and 87%,
very similar to 2d, the HOMO and LUMO are mainly located on the respectively. The maximum fluorescence quenching ability in the pres­
porphyrin and the DCV group, respectively. Strong electronic coupling ence of CN− was for DCVP 2d, which can be attributed to the presence of
between triphenylamine and porphyrin in 2a also induces a relatively a strong electron-withdrawing trifluoromethyl group, leading to the
smaller band-gap energy (Eg = 2.16 eV, see Table 1) than that of 2d (Eg maximum electron deficiency in the DCV group β-carbon. The manip­
= 2.45 eV). The Q (0,0) fluorescence emission at λ = 641 nm of 2a ulation of electron density in the DCV group β-carbon of the DCVPs is
corresponds to the bandgap energy and has a redshift of 6 nm when proven by the absorption spectra, CN− sensing ability, and theoretical
compared to that of 2d (λ = 635 nm). These theoretical results suggest calculation results. The relationships between the fluorescence titration
that modulation of charges in the β-carbon of the DCV group can occur spectral data of DCVPs 2c and 2d (F/F0 vs. [CN− ]) in THF solvent are
when regulating the electron-donating and withdrawing substituents in presented Figs. 3 and 4, respectively. The CN− detection limits were
DCVPs. calculated for DCVPs 2c and 2d based on the fluorescence titration
The DCVP was synthesized starting from 4-(dimethoxymethyl) studies. The binding constant of the complex formed in the solution was
benzaldehyde and malononitrile through the Knoevenagel condensation estimated by using the Stern-Volmer equation. The 2c and 2d binding
reaction [44] and further deportation of the acetal group with tri­ constants towards the CN− ion were found to be 30,233 M− 1 and
fluoroacetic acid [44] (Scheme 1). DCVPs 2a to 2d were synthesized 48,5375 M− 1. The CN− detection limits for DCVPs 2c and 2d are 8.9 ×
according to Lindsay’s condensation reaction [45] (Scheme 1). DCV 10− 7 M and 3.14 × 10− 8 M, respectively. The cyanide ion detection limit
aldehyde and DCVPs 2a to 2d were well characterized by NMR and of the DCVPs 2c and 2d, was compared with previously reported fluo­
MALDI-TOF MS (Supplementary Information Figs. S1–S12). rescent probes (Table S2).
The nucleophilic addition of CN− ions to the DCV group β-carbon
was investigated through 1HNMR spectroscopy on DCVP 2b and 2d and
3.2. Photophysical properties of DCVPs and their CN− sensing ability theoretical calculations. A comparison of the 1HNMR spectra of DCVP
2b and 2d before and after the addition of CN− ions is presented in Fig. 5
The electronic absorption and emission spectra of DCVPs 2a to 2d and S14. One can see that in pristine DCVP 2b, the β− carbon vinyl
were recorded in THF at room temperature (Fig. 1 and Table 1). DCVP proton appears at 8.1 ppm, whereas following the addition of the CN−
absorption was observed at λ = 406 nm for the Soret band (S0→ S2) and ions, it shifts to the up-field region at 4.75 ppm (Fig. 5). Similarly in
λ = 502, 540, 577, and 632 nm for the Q-bands (S0→ S1). The DCVP DCVP 2d the β− carbon vinyl proton appears at 10.43 ppm, whereas
emission maxima were located at λ = 635 nm and 700 nm. The DCVP 2a

Chart 1. Previously reported DCV-appended porphyrins for CN− ion sensing.

3
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

Table 1
Photophysical properties of DCVPs in THF solvent.
DCVP λab.max(nm) λem,max(nm) ФF (%) τ (ns) Theoretical band gap (eV)a

Soret band Q-bands Q (0,0) Q (0,1) HOMO LUMO Eg

2a 406 504, 544, 579, 635 641 700 18.0 8.66 5.08 2.92 2.16
2b 405 503, 544, 577, 635 640 704 9.4 9.56 5.30 2.93 2.37
2c 406 501, 535, 575, 631 635 695 13.0 9.67 5.34 2.95 2.39
2d 406 502, 540, 577, 633 635 697 11.0 9.87 5.48 3.03 2.45
a
Calculated at the B3LYP level.

Scheme 1. Synthesis of DCVPs 2a to 2d.a) Malononitrile, EtOH, Piperidine, reflux, 30 min. b) TFA, H2O, CHCl3, 0 ◦ C, 2 h. c) CHCl3, TFA, room temperature, N2, 2 h.
d) p-Chloranil, 1 h, TEA, 15min.

Fig. 1. Frontier molecular orbitals (HOMO and LUMO) and optimized structures of the DCVPs were calculated using the B3LYP level of DFT.

following the addition of the CN− ions, it shifts to the up-field region at eV, respectively and in DCVPs þ HCN are 2.54, 2.73, 2.74 and 2.74 eV,
5.12 ppm. These results indicate the addition of CN− ions to the respectively. Chart 1 and Fig. S15 and also from the DCVPs and DCVPs
DCVgroup β-carbon [41]. The frontier molecular orbitals obtained from þ HCN bandgap values indicate the interruption of the conjugation
DFT calculations of DCVPs 2a-2d and DCVPs þ HCN are shown in Chart between the porphyrin unit and DCV group.
1 and Fig. S15. In 2a the highest occupied molecular orbital (HOMO) is
located on the strong electron-donating triphenylamine and porphyrin 4. Conclusions
units, and the lowest occupied molecular orbital (LUMO) is located in
the DCV group (Chart 1). In 2a + HCN, HOMO is located on strong In conclusion, we successfully synthesized DCVPs (2a-2d) having
triphenylamine and, LUMO is located on porphyrin unit. The differences electron-donating or electron-withdrawing substituents, as cyanide-
in the HOMO–LUMO gaps of DCVPs 2a-2d are 2.16, 2.37, 2.39 and 2.45 detecting probes which have variable electrophilicity in DCV group

4
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

Fig. 2. Normalized UV-vis absorption and fluorescence emission spectra of DCVPs 2a to 2d in THF.

Fig. 3. Fluorescence spectra of DCVPs 2a (8.0 μM), 2b (7.5 μM), 2c (10.0 μM), and 2d (7.0 μM) following the addition of different anions such as Cl− , Br− , I− , ClO−4 ,
HSO−4 , NO−3 and CN− (5 eq) in THF (λex= 407 nm).

Fig. 4. Fluorescence titration spectra of DCVP 2c (10 μM) with TBACN (0 eq to 5 eq) in THF (λex = 407 nm) and the trend the fluorescence titration spectra data of
DCVP 2c (right) (F/F0 vs [CN− ]) in THF.

5
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

Fig. 5. Fluorescence titration spectra (left) of DCVP 2d (7.76 μM) with TBACN (0 eq to 5 eq) in THF (λex = 407 nm) and the trend of the fluorescence titration spectra
data of DCVP 2d (right) (F/F0 vs [CN− ]) in THF.

β-carbon. For all DCVPs, the fluorescence turn-off was observed with the Acknowledgements
increasing concentration of CN− and was found to be highly dependent
on substituents. Notably, DCVP 2d with a strong electron-withdrawing This work was financially supported by Konkuk University in 2021
substituent showed excellent detection capability for CN− with detec­ and the Korea Ministry of Environment (MOE) Graduate School
tion limits of 3.14 × 10− 8 M, much lower than cited in the WHO specialized in Integrated Pollution Prevention and Control Project. Also,
guidelines. These results demonstrate a simple strategy for developing we would like to thank the Technology Innovation Program (20015254)
high-sensitivity fluorescent probes for cyanide and can be applied to funded by the Ministry of Trade, Industry, and Energy (MOTIE, Korea).
tracking cyanide compounds in contaminated industrial wastewater.
Appendix A. Supplementary data
CRediT authorship contribution statement
General experimental methods, copies of 1H NMR and MALDI− TOF
Jiyoung Hwang: Methodology, Investigation, Writing – original mass spectra, fluorescence emission spectra, tables, and DFT data have
draft. T. Sheshashena Reddy: Conceptualization, Methodology, been provided.
Investigation, Writing – review & editing. Hyungkyu Moon: Method­ Supplementary data to this article can be found online at https://doi.
ology, Investigation. Hae Dong Lee: Methodology, Investigation. org/10.1016/j.dyepig.2023.111243.
Myung-Seok Choi: Conceptualization, Data curation, Funding acquisi­
tion, Resources, Project administration, Writing – review & editing. References

Declaration of competing interest [1] Park S− H, Kwon N, Lee J− H, Yoon J, Shin I. Synthetic ratiometric fluorescent
probes for detection of ions. Chem Soc Rev 2020;49:143–79. https://doi.org/
10.1039/c9cs00243j.
The authors declare that they have no known competing financial [2] Lee MH, Kim JS, Sessler JL. Small molecule− based ratiometric fluorescence probes
interests or personal relationships that could have appeared to influence for cations, anions, and biomolecules. Chem Soc Rev 2015;44:4185–91. https://
doi.org/10.1039/c4cs00280f.
the work reported in this paper: MYUNG-SEOK CHOI reports financial [3] Ding Y, Zhu WH, Xie Y. Development of ion chemosensors based on porphyrin
support was provided by Ministry of Trade, Industry, and Energy analogues. Chem Rev 2017;117:2203–56. https://doi.org/10.1021/acs.
(MOTIE, Korea). Myung-Seok Choi reports financial support was pro­ chemrev.6b00021.
[4] Zhou Y, Zhang JF, Yoon J. Fluorescence and colorimetric chemosensors for
vided by Korea Ministry of Environment (MOE). fluoride− ion detection. Chem Rev 2014;114:5511–71. https://doi.org/10.1021/
cr400352m.
Data availability [5] Xu Z, Chen X, Kim HN, Yoon J. Sensors for the optical detection of cyanide ion.
Chem Soc Rev 2010;39:127–37. https://doi.org/10.1039/b907368j.
[6] Wang F, Wang L, Chen X, Yoon J. Recent progress in the development of
No data was used for the research described in the article. fluorometric and colorimetric chemosensors for detection of cyanide ions. Chem
Soc Rev 2014;43:4312–24. https://doi.org/10.1039/c4cs00008k.

6
J. Hwang et al. Dyes and Pigments 215 (2023) 111243

[7] Yang Y, Zhao Q, Feng W, Li F. Luminescent chemodosimeters for bioimaging. Chem enhancement and fluorogenic discrimination between fluoride and cyanide in
Rev 2013;113:192–270. https://doi.org/10.1021/cr2004103. aqueous solution. Chem − A Eur J 2018;24:9211–6. https://doi.org/10.1002/
[8] Kulig KW. Cyanide toxicity. Atlanta GA: U.S. Department of Helath and Human chem.201800884.
Services; 1991. [27] Wade CR, Gabbai FP. Cyanide anion binding by a triarylborane at the outer rim of a
[9] Wu H, Chen M, Xu Q, Zhang Y, Liu P, Li W, et al. Switching to a “turn− on” cyclometalatedruthenium(II) cationic complex. Inorg Chem 2010;49:714–20.
fluorescent probe for selective monitoring of cyanide in food samples and living https://doi.org/10.1021/ic9020349.
systems. Chem Commun 2019;55:15137–40. https://doi.org/10.1039/ [28] Kim Y, Huh HS, Lee MH, Lenov IL, Zhao H, Gabbaï FP. Turn− on fluorescence
c9cc07492a. sensing of cyanide ions in aqueous solution at parts− per− billion concentrations.
[10] Li Q, Wang Z, Song W, Ma H, Dong J, Quan YY, et al. A novel D− π− A Chem − A Eur J 2011;17:2057–62. https://doi.org/10.1002/chem.201002861.
triphenylamine− based turn− on colorimetric and ratiometric fluorescence probe [29] Gholami MD, Liu Q, Sonar P, Manzhos S, Ayoko GA, Izake EL. Naphthalene flanked
for cyanide detection. Dyes Pigments 2019;161:389–95. https://doi.org/10.1016/ diketopyrrolopyrrole: a new functional dye based optical sensors for monitoring
j.dyepig.2018.09.074. cyanide ions in water. Adv Mater Technol 2021;2100170:1–10. https://doi.org/
[11] Sun G, Chen W, Liu Y, Jin X, Zhang Z, Su J. A novel colorimetric and fluorometric 10.1002/admt.202100170.
probe for the detection of CN− with high selectivity in aqueous media. Dyes [30] Martyanov TP, Kudrevatykh AA, Ushakov EN, Korchagin DV, Sulimenkov IV,
Pigments 2020;176:108224. https://doi.org/10.1016/j.dyepig.2020.108224. Vasil’ev SG, et al. Selective colorimetric sensor for cyanide anion based on
[12] Ozdemir A, Erdemir S. Phenanthroimidazole and dicyanovinyl− substituted 1− hydroxyanthraquinone. Tetrahedron 2021;93:132312. https://doi.org/
triphenylamine for the selective detection of CN− : DFT calculations and practically 10.1016/j.tet.2021.132312.
applications. J Photochem Photobiol Chem 2020;390:112328. https://doi.org/ [31] Paden RR, Oracion JPL, De La Rosa LB, Lavapiez MAM, Alguno AC, Deocaris CC,
10.1016/j.jphotochem.2019.112328. et al. Design and fabrication of a low− cost curcumin− based paper sensor for rapid
[13] Li Z, Dai Y, Lu Z, Pei Y, Song Y, Zhang L, et al. A photoswitchable triple “naked− eye” cyanide sensing. Mater Today Proc 2020;46:1711–7. https://doi.org/
chemosensor for cyanide anion based on Dicyanovinyl− Functionalized 10.1016/j.matpr.2020.07.374.
dithienylethene. Eur J Org Chem 2019:3614–21. https://doi.org/10.1002/ [32] Tang L, Zhou L, Liu A, Yan X, Zhong K, Liu X, et al. A new cascade reaction− based
ejoc.201900369. colorimetric and fluorescence “turn on” dual− function probe for cyanide and
[14] Li Z, Song Y, Dai Y, Pei Y, Lu Z, Guo H. Dicyanovinyl− substituted D− A type hydrazine detection. Dyes Pigments 2021;186:109034. https://doi.org/10.1016/j.
dithienylethenes: synthesis, photochromism and colorimetric sensing for cyanide dyepig.2020.109034.
anion. Opt Mater 2019;95:109235. https://doi.org/10.1016/j. [33] Milgrom RL. The colours of life: an introduction to the chemistry of porphyrins and
optmat.2019.109235. related compounds. New York: Oxford University Press; 1997.
[15] Reddy TS, Choi MS. Dicyanovinylcoumarin as a turn− on fluorescent sensor for [34] Li LL, Diau EWG. Porphyrin− sensitized solar cells. Chem Soc Rev 2013;42:
cyanide ion. J Photochem Photobiol Chem 2018;351:108–14. https://doi.org/ 291–304. https://doi.org/10.1039/c2cs35257e.
10.1016/j.jphotochem.2017.10.021. [35] Chan WL, Xie C, Lo WS, Bünzli JCG, Wong WK, Wong KL. Lanthanide− tetrapyrrole
[16] Erdemir S, Malkondu S. Cyanobiphenyl− spiropyrane and − hemicyanine complexes: synthesis, redox chemistry, photophysical properties, and photonic
conjugates for cyanide detection in organic/aqueous media through reverse ICT applications. Chem Soc Rev 2021;50:12189–257. https://doi.org/10.1039/
direction: their practical applications. Talanta 2021;231:122385. https://doi.org/ c9cs00828d.
10.1016/j.talanta.2021.122385. [36] Li Y, Lin TY, Luo Y, Liu Q, Xiao W, Guo W, et al. A smart and versatile theranostic
[17] Yang L, Li X, Qu Y, Qu W, Zhang X, Hang Y, et al. Red turn− on fluorescent nanomedicine platform based on nanoporphyrin. Nat Commun 2014;5. https://
phenazine− cyanine chemodosimeters for cyanide anion in aqueous solution and its doi.org/10.1038/ncomms5712.
application for cell imaging. Sensor Actuator B Chem 2014;203:833–47. https:// [37] Rajora MA, Lou JWH, Zheng G. Advancing porphyrin’s biomedical utility: via
doi.org/10.1016/j.snb.2014.07.045. supramolecular chemistry. Chem Soc Rev 2017;46:6433–69. https://doi.org/
[18] Wen D, Deng X, Yu Y. A novel indolium salt as a rapid colorimetric probe for 10.1039/c7cs00525c.
cyanide detection in aqueous solution. Chem Pap 2021;75:1095–102. https://doi. [38] Tanaka T, Osuka A. Conjugated porphyrin arrays: synthesis, properties and
org/10.1007/s11696− 020− 01371− 3. applications for functional materials. Chem Soc Rev 2015;44:943–69. https://doi.
[19] Sun Y, Li Y, Ma X, Duan L. A turn− on fluorescent probe for cyanide based on org/10.1039/c3cs60443h.
aggregation of terthienyl and its application for bioimaging. Sensor Actuator B [39] Zhang W, Lai W, Cao R. Energy− Related small molecule activation reactions:
Chem 2015;224:648–53. https://doi.org/10.1016/j.snb.2015.10.057. oxygen reduction and hydrogen and oxygen evolution reactions catalyzed by
[20] Sun C, Du W, Wang B, Dong B, Wang B. Research progress of near− infrared Porphyrin− and Corrole− Based systems. Chem Rev 2017;117:3717–97. https://
fluorescence probes based on indole heptamethine cyanine dyes in vivo and in doi.org/10.1021/acs.chemrev.6b00299.
vitro. BMC Chem 2020;14:1–28. https://doi.org/10.1186/ [40] Chen B, Ding Y, Li X, Zhu W, Hill JP, Ariga K, et al. Steric hindrance− enforced
s13065− 020− 00677− 3. distortion as a general strategy for the design of fluorescence “turn− on” cyanide
[21] Chen X, Nam SW, Kim GH, Song N, Jeong Y, Shin I, et al. A near− infrared probes. Chem Commun 2013;49:10136–8. https://doi.org/10.1039/c3cc46008h.
fluorescent sensor for detection of cyanide in aqueous solution and its application [41] Chahal MK, Sankar M. Porphyrin chemodosimeters: synthesis, electrochemical
for bioimaging. Chem Commun 2010;46:8953–5. https://doi.org/10.1039/ redox properties and selective “naked− eye” detection of cyanide ions. RSC Adv
c0cc03398g. 2015;5:99028–36. https://doi.org/10.1039/c5ra19847j.
[22] Liu Y, Qiu D, Pan H, Li M, Chen H, Li H. A highly selective fluorescent probe for [42] Chahal MK, Sankar M. Switching between porphyrin, porphodimethene and
colorimetric recognition of cyanide anion based on heptamethine porphyrinogen using cyanide and fluoride ions mimicking volatile molecular
cyanine− triphenylamine conjugate. J Photochem Photobiol Chem 2018;364: memory and the “NOR” logic gate. Dalton Trans 2016;45:16404–12. https://doi.
151–8. https://doi.org/10.1016/j.jphotochem.2018.06.018. org/10.1039/c6dt02506d.
[23] Sheshashena Reddy T, Maragani R, Misra R. Triarylborane substituted [43] Chahal MK, Sankar M. β− Dicyanovinyl substituted porphyrinogen: synthesis, a
naphthalimide as a fluoride and cyanide ion sensor. Dalton Trans 2016;45: reversible sensor for picric acid among explosives and a unique sensor for cyanide
2549–53. https://doi.org/10.1039/c5dt04039f. and fluoride ions by switching between various porphyrinoid states. Dalton Trans
[24] Bresner C, Haynes CJE, Addy DA, Broomsgrove AEJ, Fitzpatrick P, Vidovic D, et al. 2017;46:11669–78. https://doi.org/10.1039/c7dt01158j.
Comparative structural and thermodynamic studies of fluoride and cyanide [44] Xia WS, Kawai H, Nagamura T. Spectroscopic studies on molecular interactions of
binding by PhBMes2 and related triarylborane Lewis acids. New J Chem 2010;34: photogenerated tricyanovinylstyrylpyridinyl radicals in acetonitrile at room
1652–9. https://doi.org/10.1039/c0nj00120a. temperature. J Photochem Photobiol Chem 2000;136:35–40. https://doi.org/
[25] Turkoglu G, Ozturk T. Fluorescent small molecules with alternating 10.1016/S1010− 6030(00)00315− 4.
triarylamine− substituted selenophenothiophene and triarylborane: synthesis, [45] Littler BJ, Ciringh Y, Lindsey JS. Investigation of conditions giving minimal
photophysical properties and anion sensing studies. Dalton Trans 2022;51: scrambling in the synthesis of trans− porphyrins from dipyrromethanes and
2715–25. https://doi.org/10.1039/d1dt03681e. aldehydes. J Org Chem 1999;64:2864–72. https://doi.org/10.1021/jo982452o.
[26] Yuan M Sen, Du X, Liu Z, Li T, Wang W, Anslyn EV, et al. Di− (2− picolyl)− N−
(2− quinolinylmethyl)amine− Functionalized triarylboron: lewis acidity