Sensors and Actuators B 141 (2009) 116–123

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Sensors and Actuators B: Chemical

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

1-Arylazo-5,5-dimethyl dipyrromethanes: Versatile chromogenic

probes for anions
Shive Murat Singh Chauhan ∗ , Tanuja Bisht, Bhaskar Garg
Bioorganic Research Laboratory, Department of Chemistry, University of Delhi, Delhi-110007, India

a r t i c l e i n f o a b s t r a c t

Article history: 1-Arylazo-5,5-dimethyl dipyrromethanes (azo-DPM’s) have been synthesized by electrophilic substi-
Received 17 January 2009 tution reactions of 5,5-dimethyl dipyrromethanes in aqueous solution in 23–68% yields. The solution
Received in revised form 11 April 2009 phase binding studies of azo-DPM’s have been investigated by naked eye, absorption and proton NMR
Accepted 5 June 2009
spectroscopy. The receptors, appended with electron-withdrawing groups display enhanced affinity and
Available online 16 June 2009
selectivity for F− , H2 PO4 − and AcO− than electron-donating groups in different solvents. Furthermore,
the solvatochromic responses of 2,5-bis(4 -nitrophenyl)azo-pyrrole have been examined by visual and
Keywords:
UV–vis spectroscopy with or without structurally different anions in a variety of solvents. The present
Electrophilic substitution
Anion binding
studies of anion receptors may be used in environmental sensors, molecular electronics and development
Colorimetric sensors of molecular switches.
UV–vis spectroscopy © 2009 Elsevier B.V. All rights reserved.
Azo-coupling
Solvatochromism

1. Introduction reported that 2-arylazo-meso-octamethylcalix[4]pyrrole dyes can

be used as chromogenic anion sensors [21,22], hence the easily
The design and synthesis of neutrally charged anion receptors available 1-arylazo-dipyrromethanes might be ideal candidate for
that possess high affinities and inherent selectivity for a vari- sensing and binding of different anions.
ety of targeted anions represents a well appreciated challenge in Herein, we report the synthesis of chromogenic azo-DPM’s 2–5
supramolecular chemistry. The interest in this problem reflects in which allow not only for selective and sensitive colorimetric detec-
part the significant role played by anions in many biological and tion but also easy colorimetric differentiation of F− , H2 PO4 − and
chemical systems [1–4]. Here, materials capable of reversible anion- AcO− of different geometries.
induced color changes are particularly attractive as they require
little or no instrumentation for practical uses [5,6]. 2. Results and discussion
Dipyrromethanes have emerged as useful intermediates for the
synthesis of porphyrins [7–10], related polypyrrolic macrocycles 5,5-Dimethyldipyrromethane, 1 was synthesized by minor mod-
[11,12] and pigments [13]. In most cases, the meso position has ification in the literature procedures [23]. The reaction of 1 with
either no substituents or a single aryl or alkyl substituent. How- one equivalent of freshly prepared aryldiazonium chloride in the
ever, limited examples of 5,5-dialkyl/diaryldipyrromethanes are presence of catalytic amount of NaHCO3 afforded 1-arylazo-5,5-
available in the literature [14,15]. Apart from their synthesis lit- dimethyl dipyrromethanes, 2–5 in moderate yields (Scheme 1).
tle attention has been paid to explore these important building It is worthy to mention here that using quantitative amount
blocks as versatile anion receptors and sensors. In an elegent work of diazonium salt (1.0 equiv.) in the reaction, the formation of
[16], Dehaen and coworkers have explored the ability of dialkyl monopyrrole degradation product was not recognized, as fre-
dipyrromethanes to recognize neutral phenols in membrane sys- quently encountered with excess of aryldiazonium salts [24].
tems similar to calix[4]pyrrole [17,18]. The quinoxaline derivatives, However, the reaction of 1 with p-nitrophenyldiazonium chloride
bearing dipyrromethane substituents and 2,6-diamidopyridine (1.0 equiv.) under basic conditions gave monopyrrole degrada-
dipyrromethane hybrid macrocycles display augmented affinity tion product, 2,5-bis(4 -nitrophenyl)azo-pyrrole, 6 in significant
towards variety of anions [19,20]. Recently we and other had amount. Indeed due to the formation of this degradation product, 6
(isolated up to 20% yield), the lower yield of 1-(4 -nitrophenyl)azo-
5,5-dimethyldipyrromethane, 5 was obtained. The synthesized
∗ Corresponding author. Fax: +91 11 27666845. azo-DPM’s 2–5 were characterized by IR, UV–vis, 1 H NMR, 13 C NMR
E-mail address: [email protected] (S.M.S. Chauhan). and ESI-mass spectroscopic techniques.

0925-4005/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.snb.2009.06.013
 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123 117

Scheme 1. Diazo-coupling reaction of 5,5-dimethyl dipyrromethanes.

2.1. Anion binding studies of chromophoric azo-dipyrromethanes (5.0 × 10−5 M) of anionic guests (F− , Cl− , Br− , I− , HSO4 − , H2 PO4 −
(2–5) and AcO− ) to the investigated derivatives, 2–5 (5.0 × 10−5 M).
In the absence of anions, the spectrum of 3 is characterized by
2.1.1. Naked eye detection the presence of one absorption maximum at 388 nm. Upon addi-
The anion sensing ability of compounds 2–5 was examined on a tion of F− , the peak at 388 nm decreased while a broad shoulder
qualitative level by visual examination of the anion-induced color at 430 nm appeared. Under the same conditions, no obvious spec-
changes in the solution of sensors 2–5 (5.0 × 10−5 M in DMSO) tral changes were observed upon addition of Cl− , Br− , I− , HSO4 − ,
before and after the addition of an anions (5.0 × 10−4 M in DMSO). H2 PO4 − and AcO− . This high selectivity of 3 toward F− is presum-
All the sensors except 2 showed dramatic color responses in the ably due to the strong basicity of F− . The analogous binding pattern
presence of different anions at room temperature. For instance, the towards lighter halides, particularly fluoride and to a lesser extent
DMSO solutions of azo-sensors, 3 and 4, appended with electron- acetate was observed with azo-sensor 4.
donating (–OCH3 ) and electron-withdrawing (–C6 F5 ) substituents Different from 4, the azo-dipyrromethane, 5 resulted significant
changed from light yellow to orange color, in the presence of F− UV–vis spectral changes for F− . For instance, the UV–vis spectra of
(Fig. 1A). Equally were found to be insensitive to the addition of 5 showed a characteristic absorption maximum at 438 nm. With
a large excess of Cl− , Br− , I− , HSO4 − , H2 PO4 − and AcO− (up to the successive addition of fluoride anion, peak at 438 nm gradu-
10 equiv.). However, the addition of large excess of acetate anion ally decreased with a large bathochromic shift moving from 438
deepens the color of solution of 4. to 575 nm ( = 137 nm, Fig. 2). Meanwhile a clear isobestic point
The most remarkable color based changes were observed with was observed at 493 nm. The isobestic point in UV–vis spectra indi-
azo-sensor, 5 appended with nitrophenyl substituent (Fig. 1B). The cates that there is a balance in the solution and the complex has
addition of F− , H2 PO4 − and AcO− anions changed the color of the been formed between host and guest. The new absorption peak at
solution of 5 from yellow to blue, green and violet, respectively at 575 nm can be ascribed to the partial charge-transfer (CT) inter-
low anion concentration, suggesting the significant binding of these actions between the electron rich donor nitrogen atom of pyrrole
anions with 5. moieties and the electron-deficient p-nitrophenyl units.
Thus visual inspection of solutions of azo-DPM’s before and An important additional observation made during these exper-
after the addition of anions indicate that fluoride ion interact more iments is that the spectra as well as the color of the solution of
strongly with 3–5 due to higher electro-negativity and smaller size receptor-F− conjugates revert back to the original spectra corre-
compared to other anions [25,26]. Further, 5 proved to be a potential sponding to those receptors in the absence of anion upon addition of
chromogenic anion sensor, not only for selective colorimetric detec- small aliquots of water/methanol. This phenomenon illustrates that
tion but, at the same time, easy colorimetric differentiation of F− , the addition of a protic solvent destroys the complexation between
H2 PO4 − and AcO− , which is still a challenge for most supramolec- 5 and F− , demonstrating that interaction between 5 and F− is, in
ular chemists. essence, a hydrogen-bonding interaction.
Further, in a separate experiment, The UV–vis spectra of all
2.1.2. UV–vis spectroscopy azo-sensors 3–5 have been recorded in the presence of tetrabuty-
The complexation studies of azo-DPM’s, 2–5 were carried out lammonium hydroxide in DMSO and compared with UV–vis spectra
by UV–vis spectroscopy in DMSO at room temperature. Titrations of sensors in the presence of added salts. The results indicate that
were performed by adding aliquots of 20 ␮l of stock solutions there is significant difference (>30 nm) in the absorption spectra

Fig. 1. (A) Color changes of azo-3 (5.0 × 10−5 M) in DMSO with the addition of tetrabutylammonium anions (5.0 × 10−4 M): (a) = free receptor, (b) = fluoride, (c) = chloride,
(d) = bromide, (e) = iodide, (f) = hydrogen sulfate, (g) = dihydrogen phosphate, (h) = acetate; (B) color changes of azo-5 (5.0 × 10−5 M) in DMSO with the addition of tetrabuty-
lammonium anions (5.0 × 10−4 M); (a) = free receptor, (b) = fluoride, (c) = chloride, (d) = bromide, (e) = iodide, (f) = hydrogen sulfate, (g) = dihydrogen phosphate, (h) = acetate.
118 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123

Fig. 3. Job plots of azo-5 (at 438 nm) with F− anion. The total concentration of the
host and guest is 1.0 × 10−4 mol L−1 in DMSO.

Table 1
Association constants for azo-DPM’s, 2–5 and anions in DMSO at 22 ◦ C determined
by absorption spectroscopic titrations.

Aniona Association constants Ka /M−1

2 3 4 5
Fig. 2. The absorption spectra of azo-5 (5.0 × 10−5 M) in DMSO solution upon the
F− b 1235 1934 >105 >106
addition of 20 ␮L of stock solutions (5.0 × 10−5 M) of tetrabutylammonium fluoride.
Cl− b <50 121 185 209
Br− n.d.c n.d.c 219 386
I− n.d.c n.d.c n.d.c n.d.c
of sensors in the presence of anions and base (tetrabutylammo- HSO4 − n.d.c n.d.c n.d.c 1730
H2 PO4 − n.d.c n.d.c 2420 82,400
nium hydroxide). For instance, the UV–vis spectrum of 5 shows a
CH3 COO− n.d.c n.d.c 9825 96,600
characteristic absorption maximum at 438 nm. With the addition
a
of fluoride, a new maximum appears at 575 nm. On the other hand, Anions were used in the form of their Bu4 N+ (TBA) salts. The errors in all fits are
<15%.
when hydroxide was added in the DMSO solution of 5, the new b
Fluoride and chloride used in this assay were in trihydrated and monohydrated
peak appeared at 612 nm, suggesting binding and not deprotona- forms, respectively.
tion. c
Not determined.
Continuous variation methods were used to determine the sto-
ichiometric ratio of the complexes formed between the receptors
2–5 and the anion guests. The total concentration of the host and of anions with 4 and 5 is ascribed to the electron withdrawing
anion guest was kept constant (1.0 × 10−4 mol l−1 ) in DMSO, whilst nature of dye moieties. These moieties increase the acidity of the
the molar fraction of the guest {[G]/([H] + [G])} was continuously pyrrole NH proton, which in turn, enhance the availability of NHs
varied. Fig. 3 shows the Job plots for 5 (at 438 nm) with F− anion in for hydrogen bonding and affinity of sensors towards anions.
DMSO. When the molar fraction of the guest is 0.50, the absorption
reaches a maximum, demonstrating that receptors 5 forms a 1:1 2.1.3. Solvatochromic properties of
complex with F− anion [27]. Analogous investigations were carried 2,5-bis(4 -nitrophenyl)azo-pyrrole, 6
out on a variety of anions such as Cl− , Br− , I− , AcO− and H2 PO4 − . The The solvatochromic properties of 2,5-bis(4 -nitrophenyl)azo-
quantitative absorption spectroscopic titrations were used to deter- pyrrole, 6 was also examined at micromolar level (2.0 × 10−6 M).
mine the binding constants for 2–5 with different anions. Binding Interestingly, the degradation product, 6 showed a typical observ-
constants (Kass ) were calculated by the equation as described by the able color changes in several solvents having different polarities
Connors [28] and are summarized in Table 1. (Fig. 4). Furthermore, the addition of anions (5.0 × 10−4 M) to the
The data presented in Table 1, indicates that all sensors, 3–5 solutions of 6 (5.0 × 10−5 M) in these systems produced remarkable
display higher affinity and selectivity for fluoride anion. The color modulations. For example, the addition of F− , H2 PO4 − and
specific order of binding affinities of azo-sensors is as follows: AcO− to the acetonitrile solution of 6 changed the color of the solu-
azo-5  azo-4 > azo-3 > azo-2. Further, the selectivity trend of the tion from pink to light blue (F− ) and dark blue (H2 PO4 − and AcO− ).
binding affinity of azo-5 for different anions is in the order Similar sensing phenomenon was observed in chloroform also. The
F− > AcO− > H2 PO4 −  Cl− , Br− , I− and HSO4 − . The strong binding striking difference in color between acetonitrile and chloroform

Fig. 4. Color changes of 2,5-bis(4 -nitrophenyl)azo-pyrrole, 6 (2.0 × 10−6 M) in (a) = CH3 CN, (b) = CH2 Cl2 , (c) = THF, (d) = MeOH, (e) = acetone, (f) = CHCl3 , (g) = diethyl ether,
(h) = DMF, (i) = pyridine.
 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123 119

Fig. 5. Color changes of 2,5-bis(4 -nitrophenyl)azo-pyrrole, 6 (5.0 × 10−5 M) in (A) CH3 CN (B) CHCl3 (C) DMSO (D) CH3 COOEt with the addition of tetrabutylammonium anions
(5.0 × 10−4 M); (a) = free receptor, (b) = fluoride, (c) = chloride, (d) = bromide, (e) = iodide, (f) = hydrogen sulfate, (g) = dihydrogen phosphate, (h) = acetate.

was recognized with Cl− and HSO4 − . The addition of chloride in ace- Moving from nonpolar to polar solvents, naked eye detection of
tonitrile produced blue color in contrast to violet color, observed in 6 was performed in DMSO and ethyl acetate. In DMSO solution, 6
chloroform. Likewise, the addition of HSO4 − caused no remarkable gave dark blue color which faded to light blue, on addition of F− . The
color response in acetonitrile but in chloroform, a clear magenta addition of Cl− , Br− , I− , HSO4 − , H2 PO4 − and AcO− (up to 20 equiv.)
color was observed (Fig. 5). did not gave any color based responses. Moreover in ethyl acetate,

Fig. 6. The absorption spectra’s of 6 (5.0 × 10−5 M) in CH3 CN solution upon the addition of 20 ␮l of stock solutions (5.0 × 10−5 M) of (a) F− (b) AcO− (c) H2 PO4 − and (d) Cl− .
120 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123

the addition of F− , H2 PO4 − and AcO− changed the solution of 6 from 2.1.4. 1 H NMR spectroscopy
yellow to orange (F− , H2 PO4 − ) and brown, respectively. In order to further validate the interaction between azo-sensors
UV–vis titrations of 6 with different anions were also carried out and the selective anions, the 1 H NMR titrations were performed in
in acetonitrile. The UV–vis spectrum of 6 (5.0 × 10−5 M) in acetoni- DMSO-d6 -0.5% water with F− , H2 PO4 − and AcO− at low concen-
trile gave characteristic absorption peak at 505 nm. Upon addition tration (5.0 × 10−3 M). Specifically, upon addition of F− , AcO− , and
of F− as tetrabutylammonium salt, the absorption at 505 nm grad- H2 PO4 − to the DMSO-d6 solution of 4 and 5, the one of pyrrolic
ually decreased with the appearance of new absorption at 591 nm. NH having azo functionality at ␣-position was disappeared and not
The formation of new maxima at 591 nm was also detected in spec- reappeared during the course of titrations. The 1 H NMR spectral
troscopic titrations of 6 with AcO− and H2 PO4 − . In contrast, on changes upon addition of F− and AcO− to the DMSO-d6 solution of
the addition of Cl− , the absorption maxima shifted from 505 nm to azo-5 are shown in Figs. 7 and 8, respectively.
572 nm with remarkable decrease in absorption intensity (Fig. 6). The 1 H NMR spectra of 5 (5.0 × 10−3 M) in DMSO-d6 showed
No spectral changes were recognized with other anions, i.e. Br− , two NH resonances at ı 10.6 and 11.7 ppm in the absence of anion.
I− and HSO4 − . The observed color transitions, as well as large Upon addition of 0.2 equiv. of F− , the NH resonance of 5 at ı 11.7
bathochromic shifts induced by 6 in the presence of F− and AcO− are was disappeared and signal at ı 10.6 exhibited a downfield by ı
due to deprotonation, confirmed by recording the UV–vis spectrum 0.1 ppm. On the successive addition of aliquots of F− , the signal
of 6 in the presence of Bu4 NOH. The binding constant of degradation gradually shifted from ı 10.7 to 11.3 ppm and finally split by the
product 6 is not calculated due to its special behavior as described coupling of F− , a hallmark of strong binding [29]. Similarly, the
above. addition of AcO− to the DMSO-d6 -0.5% water solution of 5 caused a

Fig. 7. Proton NMR spectra of azo-5 (5.0 × 10−3 M) in DMSO solution at 25 ◦ C on addition of aliquots of F− (5.0 × 10−3 M).
 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123 121

Fig. 8. Proton NMR spectra of azo-5 (5.0 × 10−3 M) in DMSO solution at 25 ◦ C on addition of aliquots of AcO− (5.0 × 10−3 M).

little but significant downfield shifting of NH resonance from ı 10.6 as easy colorimetric differentiation of F− , H2 PO4 − and AcO− of dif-
to 10.9 ppm. Consistent and reproducible binding pattern was also ferent geometries. Furthermore color changes shown by 6 toward
observed with dihydrogen phosphate where the resonance of the different anions in a variety of solvents are also important from bio-
recognition points broadened with noticeable downfield shifting. logical point of view. For sensing purposes, the solvatochomic effect
These results imply that only one pyrrolic NH of sensors 4 and might have some importance and may be used to select the initial
5 is involved in hydrogen bond formation with anions. On the con- and final color of certain designed probes.
trary, the titrations of 2 and 3 with F− caused noticeable downfield Further studies on the development of water soluble azo-
shifting of both pyrrolic NH (0.2–0.3 ppm). This is in contrast to that dipyrromethane based chromogenic probes for anions are now in
observed in case of N-confused arylazocalix[4]pyrrole [30] which progress.
undergoes fluoride triggered deprotonation. Thus at low anion con-
centration, one can safely assume that binding phenomenon exists.
3. Experimental

2.1.5. Conclusion 3.1. Materials

In conclusion we have demonstrated that the easily available
1-arylazo-dipyrromethanes can be used as potential chromogenic All the anions in the form of tetrabutylammonium salts, were
anion probes. Quantitative absorption spectroscopic analysis and purchased from Sigma–Aldrich Chemical Co., stored in a desiccator
1 H NMR spectroscopy essentially confirmed this. Consequently, under vacuum containing self-indicating silica and used without
azo-5 allowed selective and sensitive colorimetric detection as well any further purification. HPLC grade solvents were used in assay.
122 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123

Pyrrole was distilled prior to use. All the other common chemicals whereupon it was cooled to room temperature and diluted with
were of analytical grade. water (10 ml). The addition of water immediately precipitate out
the 5,5-dimethyldipyrromethane which was filtered and dried.
3.2. Methods Crystallization from dichloromethane/hexane gave fine colorless
needles of 1.
Column chromatography was carried out on Merck silica gel 5,5-dimethyldipyrromethanes (1) Yield: 1.32 g (77%); m.p.
(60–120 mesh). The 1 H NMR and 13 C NMR were recorded on Bruker 55–57 ◦ C; IR (KBr pellet, cm−1 ): (3361, N–H), (2933, C C), 1 H NMR
Avance-300 (300 MHz, 75 MHz) spectrometer using tetramethylsi- (300 MHz, CDCl3 , 298 K): 1.61 (s, 6H, –CH3 ), 6.08 (s, 2H, ␤-pyrrolic),
lane (TMS) and residual solvent signal (DMSO-d6 , ı 2.49, CDCl3 , 6.1 (d, 2H, ␤-pyrrolic), 6.5 (d, 2H, ␣-pyrrolic), 7.64 (s, br, 2H, NH-
ı 7.25) as internal standard and chemical shifts (ı) are expressed pyrrole); 1 H NMR (300 MHz, DMSO-d6 , 298 K): ı 1.54 (s, 6H, –CH3 ),
in ppm. The infrared spectra were recorded on PerkinElmer spec- 5.66 (s, 2H, ␤-pyrrolic), 5.8 (d, J = 1.8 Hz, 2H, ␤-pyrrolic), 6.54 (s,
trum FT-2000 spectrometer and max are expressed in cm−1 . The 2H, ␣-pyrrolic), 10.3 (bs, 2H, NH-pyrrole); 13 C NMR (75 MHz, CDCl3 ,
electronic spectra were recorded on PerkinElmer UV-2006 UV–vis 298 K): 29.26 (–CH3 ), 35.23 (meso-C), 103.74 and 107.56 (␤-pyrrolic
spectrophotometer and the absorption maxima are expressed in CH), 117.11 and 139.08 (␣-pyrrolic CH); ESI-MS for C13 H18 N2 Na
nanometers (nm). The high resolution mass spectra (ES-HRMS) [M+Na]+ : Calcd: 225.1368, found: 225.1362.
were recorded on a VG-Fisions ‘Autospec’ spectrometer. ESI-MS
spectra were recorded on KC ESI 455-TOF mass spectrometer of 3.6.2. General procedure for the synthesis of
waters (Micromass, Manchester, UK). 1-arylazo-5,5-dimethyldipyrromethanes (2–5)
Freshly prepared solution of phenyldiazonium chloride
3.3. UV–vis titration studies (5.10 mmol) was added slowly to a cold (−10 ◦ C) solution of
5,5-dimethyldipyrromethane, 1 (870 mg, 5.00 mmol) contain-
The binding ability of azo-sensors, 2–5 and 6 for H2 PO4 − , ing catalytic amount of NaHCO3 in THF (50 ml). A dark yellow
HSO4 − , AcO− and halide anions (as tetrabutylammonium salts) to orange suspension is immediately formed. After stirring for
was investigated by UV–vis spectroscopy in DMSO and acetonitrile, 30 min, solution was diluted by water (2× 10 ml) and extracted
respectively. Stock solutions of chromogenic hosts, 2–5 and anions with ethyl acetate. Organic extracts were again washed with
were prepared by dissolution in DMSO (Each 5.0 × 10−5 M). UV–vis water and dried over anhydrous magnesium sulfate. The solvent
titrations were performed with constant host concentration and was evaporated under reduced pressure. Chromatographic purifi-
increasing concentration of anions. cations with ethyl acetate:petroleum ether, 1:10, v/v) afforded
1-arylazo-5,5-dimethyldipyrromethanes.
3.4. Determination of stoichiometry of the host–guest complex 1-(4 -Bromophenyl)azo-5,5-dimethyldipyrromethanes (2):
Yield: 406 mg (23%); m.p. 124–126 ◦ C; UV–vis (max DMSO,
The stoichiometry was determined by the continuous variation (log ε)): 388 (3.9); IR (KBr pellet, cm−1 ): 3436 (br, pyrrole NH),
method (Job’s Plot). The azo-DPM’s, 2–5 and tetrabutylammonium 3025 (CH aryl), 2925, 2853, 1627 (N N), 700, 640; 1 H NMR
salts were dissolved in HPLC grade DMSO separately at appropri- (300 MHz, DMSO-d6 298 K): 1.60 (s, 6H, –CH3 ), 5.82–5.77 (m, 4H,
ate concentrations, which were then mixed and made up with the ␤-pyrrolic CH), 6.32 (s, 1H, ␣-pyrrolic CH) 6.8 (d, J = 7.8 Hz, 2H,
solvent to control the concentrations. The sum of the total con- aryl CH), 7.5 (d, J = 7.8 Hz, 2H, aryl CH), 10.3 (s, 1H, NH-pyrrole),
centration of the host [H]T and anion [A− ]T namely [H]T + [A− ]T 10.9 (s, 1H, NH-pyrrole); 13 C NMR (75 MHz, CDCl3 , 298 K): 25.89
was maintained to be 0.1 mM in DMSO. At the same time, the (–CH3 ), 35.29 (meso-C), 93.16 CH, 102.14 CH, 103.85 CH, 105.35
ratio [H]T /[A− ]T was varied from 1:9 to 9:1. After recording the CH, 114.87 ␣-pyrrolic CH, 121.53 CH, 124.17 CH, 135.91 C, 137.23 C,
UV–vis spectrum of these solutions, the appropriate absorbance 140.62 C, 146.31 C, 154.89 C; ES-HRMS for C17 H16 BrN4 [M−H]− :
values were plotted against the mole fraction of the anions. The Calcd: 355.0558, found: 355.0560.
maximum was observed at [A− ]T /[H]T + [A− ]T 0.5 which implied 1-(4 -Methoxyphenyl)azo-5,5-dimethyldipyrromethane (3):
the stoichiometry to be 1:1 for different anions. Yield: 1.0 g (68%); m.p. 163–165 ◦ C; UV–vis (max DMSO, (log ε)):
391 (4.2); IR (KBr pellet, cm−1 ): 3443 (br, pyrrole NH), 3099 (–CH
3.5. 1H NMR titration studies aryl), 2968, 1607 (N N), 1303, 1157, 1030 (–CH3 ), 767, 551; 1 H NMR
(300 MHz, DMSO-d6 , 298 K) 1.63 (s, 6H, –CH3 ), 3.79 (s, 3H, –OCH3 ),
The 1 H NMR titration experiments were carried out in the 5.80 (s, 2H, ␤-pyrrolic CH), 5.88 (s, 2H, ␤-pyrrolic CH), 6.62 (s,
DMSO-d6 -0.5% water solution. A 5.0 × 10−3 M solution of 2–5 in 1H, ␣-pyrrolic CH) 7.0 (d, J = 8.0 Hz, 2H, aryl CH), 7.6 (d, J = 8.0 Hz,
DMSO-d6 (0.5 ml) was prepared in 5-mm NMR tube. A 5.0 × 10−3 M 2H, aryl CH), 10.5 (s, 1H, NH-pyrrole), 11.1 (s, 1H, NH-pyrrole);
solution of anion in DMSO-d6 (1.0 ml) was prepared in a 1 ml volu- 13 C NMR (75 MHz, CDCl , 298 K): 29.36 (–CH ), 35.39 (meso-C),
3 3
metric flask. An initial NMR spectrum of sensor was recorded and 60.82 (OCH3 ), 104.64 CH, 105.68 CH, 109.25 CH, 109.10 CH, 115.62
the initial chemical shift of NH protons was determined. Control CH, 122.49 CH, 123.47 CH, 136.18 C, 136.72 C, 145.42 C, 145.49 C,
studies indicated that in the absence of binding partner, the chem- 157.48 C; ES-HRMS for C18 H19 N4 O [M−H]− : Calcd: 307.1559, found:
ical shifts of the NH protons were not concentration dependent. 307.1564.
The solution of anion was then added in portions and spectra were 1-(1 2 3 4 5 -Pentafluoro)azo-5,5-dimethyldipyrromethane (4):
recorded after each addition. The aliquots were added until no fur- Yield: 548 mg (30%); m.p. 114 ◦ C; UV–vis (max DMSO, (log ε)):
ther change in the chemical shifts of the NHs was observed. The 375 (3.7); IR (KBr pellet, cm−1 ): 3430 (br, pyrrole NH), 1623
temperature of the NMR probe was 20–21 ◦ C. (N N), 751, 632; 1 H NMR (300 MHz, DMSO-d6 , 298 K): 1.68 (s, 6H,
–CH3 ), 5.84–6.55 (m, 4H, ␤-pyrrolic CH), 6.85 (s, 1H, ␣-pyrrolic
3.6. Synthesis CH), 10.8 (s, 1H, NH-pyrrole), 11.6 (bs, 1H, NH-pyrrole); 13 C NMR
(75 MHz, CDCl3 , 298 K): 28.32 (–CH3 ), 35.12 (meso-C), 103.15 CH,
3.6.1. Synthesis of 5,5-dimethyldipyrromethane (1) 103.99 CH, 107.15 CH, 109.11 CH, 118.12 ␣-pyrrolic CH, 137.98 C,
To a solution of acetone (20.0 mmol, 1.47 ml) and 138.75 C, 142.22 C, 146.89 C, 147.02 C, 148.56C, 152.55 C; ES-HRMS
[Bmim]BF4 (5.0 ml), pyrrole (70.0 mmol, 4.9 ml) was added drop- for C17 H12 N4 F5 [M−H]− : Calcd: 367.0982, found: 367.0979.
wise at 0 ◦ C. The progress of the reaction was monitored by thin 1-(4 -Nitrophenyl)azo-5,5-dimethyldipyrromethane (5): Yield:
layer chromatography. The reaction was stirred at 0 ◦ C for 2 h 528 mg (33%); m.p. 138–140 ◦ C; UV–vis (max DMSO, (log ε)): 438
 S.M.S. Chauhan et al. / Sensors and Actuators B 141 (2009) 116–123 123

(4.4); IR (KBr pellet, cm−1 ): 3443 (br, pyrrole NH), 3035 (CH aryl), [13] J. Chen, A. Burghart, A. Derecski-Kovacs, K. Burgess, 4,4-Difluoro-4-bora-
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298 K) 1.66 (s, 6H, –CH3 ), 5.83 (s, 1H, ␤-pyrrolic CH), 5.88 (s, precursor for the synthesis of calix[4]phyrins and pseudocorroles using Mac-
1H, ␤-pyrrolic CH), 6.0 (d, J = 3.9 Hz, 1H, ␤-pyrrolic CH), 6.64 (s, Donald [2 + 2] condensations, Tetrahedron Lett. 46 (2005) 6067–6070.
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symmetry of the calix[4]pyrrole cavity on sensitivity and selectivity of poten-
28.69 (–CH3 ), 35.95 (meso-C), 103.37 CH, 104.74 CH, 108.25 CH, tiometric sensors for neutral nitrophenols, Mat. Sci. Eng. (C) 18 (2001) 223–228.
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Calcd: 322.1304, found: 322.1300.
[19] J.L. Sessler, H. Maeda, T. Mizuno, V.M. Lynch, H. Furuta, Quinoxaline-
2,5-Bis(4 -nitrophenylazo)pyrrole (6): Yield: 314 mg (20%); m.p. oligopyrroles: improved pyrrole-based anion receptors, Chem. Commun.
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lets, cm−1 ): 3482, 3366, 2927, 1631, 1592, 1476, 1443, 1302, 1179, [20] J.L. Sessler, E. Katayev, G.D. Pantos, P. Scherbakov, M.D. Reshetova, V.N.
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1110, 841, 751; 1 H NMR (300 MHz, CDCl3 , 298 K): 9.00 (bs, 1H, NH- of 2,6-diamidopyridine dipyrromethane hybrid macrocycles, J. Am. Chem. Soc.
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CH), 5.96 (s, 2H, ␤-pyrrolic CH); ES-HRMS for C16 H10 N7 O4 [M−H]− : [21] R. Nishiyabu, M.A. Palacios, W. Dehaen, P. Anzenbacher Jr., Synthesis, structure,
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the Council of Scientific and Industrial Research for financial assis- [25] C.B. Black, B. Andrioletti, A.C. Try, C. Ruiperez, J.L. Sessler, Dipyrrolylquionox-
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[7] B.J. Littler, Y. Ciringh, J.S. Lindsey, Investigation of conditions giving minimal S.M.S. Chauhan received his Ph.D. in chemistry from Central Drug Research Insti-
scrambling in the synthesis of trans-porphyrins from dipyrromethanes and tute, Lucknow. His major research interests are the development of chemical models
aldehydes, J. Org. Chem. 64 (1999) 2864–2872. of cytrochrome P450, flavin and pteridine monooxygenases and their applications
[8] L.H. Yu, J.S. Lindsey, Investigation of two rational routes for preparing p- in the biomimetic oxygenations and oxidations of organic substrates. He has pub-
phenylene-linked porphyrin trimers, Tetrahedron 57 (2001) 9285–9298.
lished over 100 papers in national and international journals. He is active member
[9] H. Ogura, F.A. Walker, Synthesis of a trans-disubstituted tetraarylporphyrin with
of many chemical societies and executive member of Indian society of chemists and
two sterically large groups near the potential sites of axial ligation: an appli-
cation of MacDonald ‘2 + 2’ porphyrin synthesis in aqueous anionic surfactant, biologists.
Inorg. Chem. 40 (2001) 5729–5732.
T. Bisht received her M.Sc. in organic chemistry from Kumaun University in 2002. She
[10] A.N. Cammidge, O. Ozturk, Controlled scrambling in porphyrin synthesis-
is currently pursuing her Ph.D. in chemistry in University of Delhi, Delhi. Her research
selective synthesis of 5,10-disubstituted porphyrins, Tetrahedron Lett. 42
work is focused on development of new sensors for anions and non-covalent inter-
(2001) 355–358.
[11] C.V. Asokan, S. Smeets, W. Dehaen, Sterically encumbered triarylcorroles from actions in supramolecular chemistry.
aryldipyrromethanes and aromatic aldehydes, Tetrahedron Lett. 42 (2001)
B. Garg received his M. Phil. in organic chemistry from Delhi University in
4483–4485.
2004–2005. He is currently pursuing his Ph.D. in chemistry in University of Delhi,
[12] V. Král, J.L. Sessler, R.S. Zimmerman, D. Seidel, V. Lynch, B. Andrioletti, Cal-
ixphyrins: Novel macrocycles at the intersection between porphyrins and Delhi. His research work is focused on development of new sensors for anions and
calixpyrroles, Angew. Chem. Int. Ed. 39 (2000) 1055–1058. non-covalent interactions in supramolecular chemistry.