A diketopyrrolopyrrole-based colorimetric and fluorescent probe for cyanide detection

Article abstract of DOI:10.1002/asia.201101038

Red means CN: A new type of diketopyrrolopyrrole-based chromophore has been synthesized as a colorimetric and fluorescent probe for the detection of cyanide using only two reaction steps. Through the addition of cyanide to the chromophore, the fluorescence emission and color were greatly changed in a highly sensitive and selective manner. Copyright

Full text of DOI:10.1002/asia.201101038

DOI: 10.1002/asia.201101038
A Diketopyrrolopyrrole-Based Colorimetric and Fluorescent Probe for
Cyanide Detection
Young-Hwan Jeong, Chi-Hwa Lee, and Woo-Dong Jang*[a]
The development of anion detection systems has received
increasing attention because anions play fundamental and
very important roles in chemical, biological, industrial, and
environmental processes.[1] In particular, cyanide is an im-
portant chemical in various industrial processes, such as the
synthesis of fibers, resins and herbicides and in gold extrac-
tion.[2] In addition, cyanide is well known as one of the most
toxic species and is extremely harmful to mammals.[3] Any
accidental release of cyanide to the environment causes seri-
ous problems.[4] Therefore, various cyanide detection meth-
ods, that is, potentiometry, voltammetry, gas chromatogra-
phy, quartz crystal microvalence, and so on, have been de-
veloped.[5] Although those traditional methods successfully
exhibited high sensitivity and selectivity, complicated set up
with operation technique and time-consuming processes
were often needed for accurate measurement of cyanide
concentration. Compared to the traditional methods, colori-
metric and fluorescence-based chemosensors are much more
convenient and cost effective.[6] In this regard, we have re-
cently reported a carbazole-based fluorescent probe for cya-
nide detection, which exhibited high sensitivity and selectivi-
ty to cyanide through the a ligand-exchange process.[7] How-
ever, an improvement in the carbazole-based system is re-
quired because the carbazole moiety has a relatively low
fluorescence quantum yield. Also, a colorimetric detection
system has great merit due to its simplicity and cost effec-
tiveness.
Along these lines, we have aimed to develop a new type
of cyanide sensing probe using diketopyrrolopyrrole (DPP)
derivatives. DPP and its derivatives represent an important
class of high-performance pigments; they are used in paints,
color inks, and plastics owing to their brilliant color and ex-
ceptional high stability upon exposure to light, weather, and
heat.[8] Recently, modified DPPs have been developed as
functional materials for optical and electronic devices, in-
cluding field-effect transistors (FETs),[9] polymer solar cells
(PSCs),[10] organic light-emitting diodes (OLEDs),[11] organic
photorefractives,[12] and applications requiring two-photon
absorption,[13] owing to their large extinction coefficients
and high fluorescence quantum yields. Therefore, DPP de-
rivatives would also be good candidates for the design of
chemosensors. However, very few examples of DPP-based
chemosensors have been reported.[14] In this context, we
report herein a new type of DPP-based chemosensor (1) for
cyanide using colorimetric as well as fluorescence detection.
As shown in Scheme 1, the synthesis of 1 requires only
two reaction steps from known compounds. The cycloaddi-
tion reaction of diisopropyl succinate to bromobenzonitrile
Scheme 1. Synthesis of 1. Reagents and conditions: i) Na, FeCl3, diiso-
propyl succinate, tert-amylalcohol, 1208C, 24 h; ii) N-dimethylaminopyri-
dine (DMAP) and di-tert-butyl dicarbonate, THF, 258C, 12 h; iii) benzyl
bromide, K2CO3, DMF, 1408C, 3 h.
resulted in dibromo-DPP (2) as a red powder. Because of
strong hydrogen bond formation, 2 was insoluble in most or-
ganic solvents. The protection of NH groups in 2 using di-
tert-butyldicarbonate simply generated 1, which was unam-
biguously characterized by 1H and 13C NMR spectroscopy
and ESI-MS analyses. When the NH groups in 2 were pro-
tected with tert-butoxylcarbonyl (Boc) groups, the maximum
absorption band appeared at 442 nm. In this process, the
Boc group enhances solubility and changes the electronic
density of DPP backbone. In fact, 2 has negligible fluores-
cence emission, whereas 1 exhibited strong absorption
around 442 nm and strong fluorescence emission around
512 nm with very high quantum yield (F=67%). The quan-
tum yield was determined using Coumarin6 as a reference
(F=0.78 in ethanol).[15]
[a] Y.-H. Jeong, C.-H. Lee, Prof. W.-D. Jang
Department of Chemistry, College of Science, Yonsei University
262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea)
Fax : (+82)2-364-7050
E-mail: wdjang@yonsei.ac.kr
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amount of cyanide was added to the CH2Cl2 solution of 3,
thus indicating that the carbamate groups play a key role in
cyanide detection. Considering the molecular structure of 1,
the carbonyl carbon atom in the lactam ring would be the
most electron-deficient site due to the introduction of an
electron-withdrawing carbamate group onto the neighboring
nitrogen atom. Therefore, we expected that cyanide can
attack this carbonyl carbon atom due to its high nucleophi-
licity (Scheme 2).
To confirm the exact molecular structure of the cyanide
adduct, 1H and 13C NMR spectroscopy titration studies of
cyanide to 1 were carried out. Because only three different
kinds of protons, that is, two different phenyl and one Boc
proton, exist in 1, the 1H NMR spectrum should be very
simple. In fact, only two singlet peaks were observed in the
1H NMR spectrum of 1, where the two kinds of phenyl pro-
tons completely overlapped to generate
a singlet at
7.61 ppm. As a result of cyanide addition to 1, the singlet
signal of the phenyl protons became a very complicated
multiplet with an upfield shift, indicating a change of elec-
tronic environment (Figure 2a). However, the exact molecu-
Figure 1. Change in a) absorption and b) fluorescence (lex =450 nm)
emission of 1 (10 mm) in CH2Cl2 upon addition of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9,
and 10 equiv CNÀ.
Very interestingly, the strong fluorescence emission
around 512 nm completely disappeared after the addition of
cyanide as its tetrabutylammonium (TBA) salt (Figure 1).
The solution color also immediately changed to red after
the addition of cyanide (Scheme 2). Absorption and fluores-
Scheme 2. Proposed mechanism and green to red color change of 1 by
CNÀ addition.
Figure 2. Partial a) 1H and b) 13C NMR spectral changes (400, 100 MHz
cence spectral changes of 1 in CH2Cl2 (10 mm) were exam-
ined by successive addition of cyanide (Figure 1), which re-
sulted in a dramatic decrease of the strong fluorescence
emission around 512 nm and complete disappearance after
the addition of 10 equivalents of cyanide. The absorption
around 442 nm also gradually decreased, with increasing ab-
sorption around 550 nm.
In relation with this, DPP with benzyl protection was pre-
pared as a control compound (3). Compound 3 also showed
strong florescence emission around 512 nm. However, the
emission intensity was not changed even if a large excess
respectively, CDCl3, 298 K) of 1 (17.2 mm) upon addition of CNÀ.
1
lar structure was not directly determined by H NMR spec-
troscopy because of the small number of proton signals in 1.
On the other hand, the addition of cyanide to 1 was directly
observed by 13C NMR spectroscopy. By addition of cyanide,
the signal of the carbonyl carbon atom in the lactam ring
(159.12 ppm) completely disappeared, and two new signals
appeared at 128.02 and 28.26 ppm, which can be assigned to
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A Colorimetric and Fluorescent Probe for Cyanide Detection
nitrile (k’) and neighboring carbons (g’), respectively
(Scheme 2 and Figure 2b).
phate were smaller than that for cyanide, where the fluores-
cence-based responsiveness to cyanide was 170-fold greater
than that to fluoride (Figure 3 f). Further, the increase in ab-
sorption around 580 nm only occurred after the addition of
cyanide. Therefore, we can utilize a ratiometric method for
the detection of cyanide using absorption intensity at 448
and 581 nm. Using this method, we could obtain a 12-fold
greater selectivity for cyanide compared to that of fluoride.
Because 1 exhibited sufficiently high selectivity to cya-
nide, the cyanide-concentra-
In order to evaluate the selectivity of 1 to cyanide, solu-
tions of 1 in CH2Cl2 (10 mm) each containing 10 equivalents
of one of various anionic species as (TBA salts of CNÀ, FÀ,
À
À
À
À
ClÀ, BrÀ, IÀ, ClO4 , NO3 , H2PO4 , HSO4 , AcOÀ, SCNÀ,
and SHÀ) were incubated at 258C for 10 min, and then the
colorimetric and fluorescence changes were observed
(Figure 3). Of various anions, only cyanide induced strong
tion-dependent
fluorescence
change of 1 has been examined.
The fluorescence emission in-
tensity gradually decreased with
the addition of cyanide to 1. As
shown in Figure 4, the fluores-
cence intensity clearly shows
a linear dependency on cyanide
concentration up to two equiva-
lents of cyanide addition. This
clear relationship between the
fluorescence intensity and cya-
nide concentration could be uti-
lized for direct determination
of cyanide concentration with
a
micromolar level detection
limit.
In summary, we have de-
signed a new DPP-based dye,
which emitted strong fluores-
cence around 512 nm with
a high fluorescence quantum
yield (F=67%). Upon the ad-
dition of cyanide to the dye so-
lution, the fluorescence emis-
sion completely disappeared
with
a strong color change.
Owing to the high quantum
yield of the dye, very high se-
lectivity and sensitivity to cya-
nide have been achieved. Such
Figure 3. Absorption and fluorescence emission responses to various anionic species (10 equiv) in CH2Cl2.
a,b) Visible changes of color (a) and fluorescence emission (b), c,d) spectral changes of absorption (c) and
fluorescence emission (d), and e,f) ratios of absorption between 448 and 581 nm (e) and fluorescence emission
À
responses upon excitation at 450 nm (f). 1 blank, 2 CNÀ, 3 FÀ, 4 ClÀ, 5 BrÀ, 6 IÀ, 7 ClO4À, 8 NO3À, 9 H2PO4
10 HSO4À, 11 AcOÀ, 12 SCNÀ, 13 SHÀ.
,
color change from green to red. Under UV irradiation by
a UV lamp (ex. 350 nm, VILBER LOURMAT, VL-4LC),
1 exhibited strong green fluorescence, which disappeared
after the addition cyanide, indicating the high selectivity of
1 to cyanide. To obtain detailed information about cyanide
selectivity, absorption and emission spectra of 1 in CH2Cl2
containing various anions were recorded. As shown in
Figure 3, only the solution containing cyanide shows com-
plete disappearance of absorption and fluorescence emission
around 448 and 512 nm, respectively. In the spectroscopic
observation, fluoride and phosphate also showed slight de-
creases in absorption and fluorescence emission. However,
the relative responsiveness values for fluoride and phos-
Figure 4. Fluorescence response of 1 (20 mm) at 514.5 nm with varying
CNÀ concentration (within 10 min in CH2Cl2 with excitation 450 nm).
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strong fluorescence and color changes may provide a new
foundation for the design of stimuli-responsive functional
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Experimental Section
Measurements
UV absorption spectra were recorded on a JASCO model V-660 spec-
trometer. Fluorescence emission spectra were recorded on a JASCO
1
model FP-6300 spectrometer. H and 13C NMR spectra were recorded on
a Bruker Avance DPX 400 and DPX 250 spectrometer at 258C in
CDCl3. ESI-MS measurement was performed at the Thermo Finnigan
LCQ Deca XP instrument (San Jose, CA).
Synthesis
2: Suspension of sodium (1.26 g, 54.94 mmol) and FeCl3 (catalyst, 0.1 g)
in dry tert-amyl alcohol (30 mL) was heated to 908C under N2 until the
sodium was dissolved. The mixture was cooled to 508C, 4-bromobenzoni-
trile (5 g, 27.47 mmol) was added, and then the mixture was heated to
908C. A solution of succinic acid diisopropyl ester (2.22 g, 10.99 mmol) in
dry tert-amyl alcohol (10 mL) was added dropwise over a period of 1 h.
After standing for 24 h, acetic acid (10 mL) was added and the mixture
was further heated to 1208C for 1 h. The resulting precipitate was filtered
and washed with hot water and hot methanol repeatedly and dried under
vacuum to obtain a red solid.
Compound 3 was synthesized by literature procedure.[16]
1: Compound 2 (3 g, 6.72 mmol) in dry THF (100 mL) was added to
&ok?&s 4-dimethylaminopyridine (DMAP, 2.05 g, 16.81 mmol) and di-
tert-butyldicarbonate (7 g, 33.62 mmol). The reaction mixture was stirred
at room temperature with the exclusion of atmospheric moisture over-
night. Subsequently, the reaction mixture was poured under stirring into
500 mL of distilled water. The precipitated brown solid was isolated by
filtration; the residue was washed with cold water and dried under
vacuum at room temperature. The crude product was dissolved in di-
chloromethane (100 mL) and passed through celite. The solution was
washed with water (50 mL) and dried over anhydrous MgSO4. Then the
solvent was evaporated and the product was recrystallized from CH2Cl2/
methanol (&?&:&?&), yielding 3.91 g (90%) product. UV/Vis: lmax
=
445 nm. 1H NMR (400 MHz, CDCl3): d=7.62 (s, aromatic H, 8H),
1.44 ppm (s, CH3H, 18H), 13C NMR (100 MHz, CDCl3, 258C): d=159.12,
148.00, 145.32, 131.77, 129.90, 127.00, 126.30, 112.59, 85.76, 27.62 ppm;
ESI-MS: m/z calcd. for C28H26Br2N2O6 (MC+): 644.02; m/z is not experi-
mentally found: Boc-moieties are removed during measurement and m/z
for C23H18Br2N2O4 (MC+) is found: calcd. 545.20 [M-Boc]; found 545.28.
1+CNÀ: 1H NMR (400 MHz, CDCl3, 258C): d=7.29–7.71 (m, aromatic
H, 8H), 1.33, 1.27 (s, CH3H, 18H), 13C NMR (100 MHz, CDCl3, 258C):
d=149.70, 131.40, 131.29, 130.70, 130.13, 128.61, 127.97, 106.55, 84.39,
28.26, 27.76 ppm.
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Keywords: colorimetric
diketopyrrolopyrrole · fluorescent probes · sensors
probes
·
cyanides
·
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Revised: February 16, 2012
Published online: && &&, 0000
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Fluorescent Probes
Young-Hwan Jeong, Chi-Hwa Lee,
Woo-Dong Jang*
&&&& — &&&&
A Diketopyrrolopyrrole-Based Colori-
metric and Fluorescent Probe for Cya-
nide Detection
Red means CN: A new type of diketo-
pyrrolopyrrole-based chromophore has
been synthesized as a colorimetric and
fluorescent probe for the detection of
cyanide using only two reaction steps.
Through the addition of cyanide to the
chromophore, the fluorescence emis-
sion and color were greatly changed in
a highly sensitive and selective
manner.
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www.chemasianj.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!