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COMMUNICATION www.rsc.org/chemcomm | ChemComm
Pyrrolidine constrained bipyridyl-dansyl click fluoroionophore
as selective Al3+sensorw
Debabrata Maity and T. Govindaraju*
Received 25th February 2010, Accepted 28th April 2010
First published as an Advance Article on the web 18th May 2010
DOI: 10.1039/c0cc00119h
A pyrrolidine constrained bipyridyl-dansyl (ionophore-fluorophore)
conjugate with triazole linker was synthesised through click
chemistry. The fluoroionophore serves as a selective ratiometric
Published on 18 May 2010 on http://pubs.rsc.org | doi:10.1039/C0CC00119H
and colorimetric chemosensor for Al3+ based on internal charge
transfer (ICT).
Aluminium is the third most prevalent element and the most
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abundant metal in the biosphere (approximately 8% of total
mineral components). Environmental acidification due to
increased solubility of Al minerals at lower pH increases the
amount of available Al3+ which is deadly to growing plants.1
Aluminium can be toxic to humans in excessive amounts and
even in small amounts if deposited in the brain. Excess
aluminium is acquired by the use of antiperspirants and
deodorants, aluminium cookware, cans, bleached flour, antacids
and drinking water supplies. According to a WHO report the
average daily human intake of aluminium is approx. 3–10 mg day1.
Tolerable weekly aluminium intake in the human body is
estimated to be 7 mg kg1 body weight.2 Many symptoms of
aluminium toxicity mimic those of Alzheimer’s disease
and osteoporosis.3 Colic, rickets, gastrointestinal problems,
interference with the metabolism of calcium, extreme nervousness,
anemia, headaches, decreased liver and kidney function,
memory loss, speech problems, softening of the bones, and
aching muscles can all be caused by aluminium toxicity.3,4 At
present, the main methods for aluminium detection are graphite
furnace atomic absorption spectrometry and inductively
coupled plasma atomic emission spectrometry. These techniques
are relatively complex and involve expensive instrumentation.
The fluorescent chemosensors have recently attracted significant
interest because of their potential application in medicinal and
environmental research.
In this communication, we report the synthesis and photo-
physical behavior of pyrrolidine constrained bipyridyl-dansyl
(BD) click ligand 1 for selective detection of Al3+ based on
internal charge transfer (ICT) mechanism. Ratiometric sensors
for various metal ions based on internal charge transfer (ICT)
have been reported in the recent literature.5 Ratiometric
analysis means the changes in ratio of intensities of absorption
or emission at two wavelengths which minimize the error arise
from the physical or chemical fluctuations in the sample.
Ratiometric fluorescent probes can do signal rationing to
Bioorganic Chemistry Lab, New Chemistry Unit, Jawaharlal Nehru
Centre for Advanced Scientific Research, Jakkur, Bangalore-560064,
India. E-mail: tgraju@jncasr.ac.in; Fax: +91 80 22082599;
Tel: +91 80 22082969
w Electronic supplementary information (ESI) available: Experimental
procedure, additional UV-Vis and fluorescence spectra, mass, IR and
NMR spectra, job plots and TGA data. See DOI: 10.1039/c0cc00119h
This journal is 
c The Royal Society of Chemistry 2010
increase the dynamic range and provide built-in-correction
for environmental facts. The color change would be useful not
only for the ratiometric method of detection but also for rapid
visual sensing. To the best of our knowledge only a few
fluorescent sensors have been reported for Al3+ with moderate
success.6
Bidentate heteroaromatic ligands 2,2 0 -bipyridine and 1,10-
phenanthroline are among the best known coordination
agents for many metal ions. These multidentate nitrogen
ligands generally afford high binding affinities for metal ions
due to the chelation effect. Keeping this in mind, we have
designed bipyridyl-dansyl based ligand (BD 1) as an ionophore–
fluorophore (fluoroionophore) conjugate for the selective
detection of Al3+. Fluorescent dansyl moiety was incorporated
because of its characteristic behaviour as a reporting and
binding unit to metal ion.7 The synthesis of BD 1 was achieved
through a click chemistry approach. The 1,2,3-triazole frame-
work formed by the click reaction between alkyne and azide
have been reported with anion and cation binding properties.8
BD 1 was accessed through a simple and straight forward
synthetic route (Scheme 1). The click compound (pyrrolidinyl-
triazolyl-bipyridine) obtained from azide 29a and alkyne 39b
was condensed with dansyl chloride to obtain BD 1 in
excellent yield (ESIw).
The photophysical properties of BD 1 were investigated
with absorption and fluorescence studies upon addition of
several metal ions such as Li+, Na+, K+, Ag+, Mg2+, Co2+,
Ba2+, Sr2+, Mn2+, Fe2+, Ni2+, Cu2+, Hg2+, Pb2+, Cd2+,
Zn2+, In3+ and Al3+ in acetonitrile (Fig. 1). The emission
spectrum of free BD 1 exhibits a band with maxima positioned
around 532 nm on excitation at 350 nm. The examined alkali
and alkaline earth metals exhibited no changes relative to BD
1, whereas d10 transition metal ions Zn2+, Cd2+, Ag+, Hg2+,
Pb2+ quench the emission intensity to a different extent than
the rest of the transition metal ions used to quench the
Scheme 1 (i) CuI, DIPEA, Toluene-tBuOH (4 : 1), (96%); (ii)
TFA-CH2Cl2 (1 : 1), (98%); (iii) Dansyl chloride, TEA, DMF, (98%).
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emission intensity (Fig. 1). Interestingly Al3+ showed distinct

behaviour with quenching of emission intensity at 532 nm and
the appearance of a new peak at 446 nm. This blue shift was
accompanied by enhanced fluorescence intensity. Next, change
in fluorescence behaviour of BD 1 was studied as a function of
Al3+ concentration (Fig. 2). Initially, quenching of the emission
intensity around 532 nm due to binding of Al3+ to –N(CH3)2
of dansyl moiety reduced the electron transfer, thus suppressing
the ICT process and causing the blue shift in absorption
(ESIw) and emission spectra. Further coordination of Al3+
to nitrogen atoms on the bipyridyl-triazole moiety suppressed
the PET quenching process, thus leading to an enhancement in
the emission intensity. Emission intensity around 446 nm
Published on 18 May 2010 on http://pubs.rsc.org | doi:10.1039/C0CC00119H

increased and attained saturation on reaching 1 : 1 ratio of

BD 1 : Al3+. The host–guest complex formation via coordination
of Al3+ with BD 1 occurred through two N-atoms on bipyridyl,
Fig. 2 Fluorescence spectra of BD 1 (100 mM) in CH3CN upon
one each from the triazole ring and the dansyl ring. The Job
addition of Al(ClO4)3 (0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500
plot showed (ESIw) a 1 : 1 stoichiometric complexation
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and 1000 mM) with an excitation of 350 nm. Inset: Ratiometric

between BD 1 and Al3+. The association constant (log Ka) fluorescence intensity [I446/I532] as a function of [Al3+].
of BD 1 for Al3+ was calculated to be 3.94 based on the
fluorescence changes of BD 1 upon gradual addition of the
Al3+ (ESIw).
To utilize BD 1 as an ion-selective fluorescence chemosensor
for Al3+, the effect of competing metal ions was studied. For
this purpose, BD 1 was treated with 1 eqv. of Al3+ in the
presence of other metal ions of the same concentration.
Relatively low interference was observed for the detection of
Al3+ in the presence of other metal ions (Fig. 3). The BD 1
responses for Al3+ in the presence of Fe2+, Co2+, Ni2+,
Zn2+, Cd2+ and Pb2+ are relatively low but clearly detectable.
In the case of Cu2+ and In3+, quenching of the fluorescence
signal was observed. Thus BD 1 can be used as a selective
fluorescent sensor for Al3+ in the presence of most competing
metal ions.
Fig. 3 Relative fluorescence intensities of BD 1 and its complexation
The change in the emission colour of BD 1 was visible to the
with Al3+ in the presence of various other metal ions. Dark grey bar:
naked eye under UV light at low concentrations (mM) of Al3+.
BD 1 (100.0 mM) with 1 eqv. of metal ion stated. Light grey bar:
At a higher concentration (mM) of Al3+ BD 1 gave colour 100.0 mM of BD 1 and 1 eqv. of Al3+ with 1 eqv. of metal ions stated
changes in the visible light region (ESIw), which is corresponding (for Al3+ effect 2 eqv. of Al3+) (El = 446 nm). The responses of the
to a new peak, positioned around 520 nm in the absorption BD 1 to Al3+, in the absence of competing ions, is included as
controls, dark bar, no metal ion added, light bar, 100.0 mM of ligand
1 with 1 eqv. of Al3+.

spectrum (Fig. 4). Higher concentrations of Al3+ can be easily

Fig. 1 Fluorescence spectra of BD 1 (100.0 mM) and on addition of
salts of Li+, Na+, K+, Ag+, Mg2+, Co2+, Ba2+, Sr2+, Mn2+, Fe2+,
Ni2+, Cu2+, Hg2+, Pb2+, Cd2+, Zn2+, In3+ and Al3+ (1.0 eqv.) in
CH3CN.
detected by observing the change in colour of BD 1 solution by
naked eye in visible light. A similar absorption band in the
range of 400–600 nm was not observed in the absorption
spectra of different concentrations of Al(ClO4)3 recorded in
the absence of the ligand (ESIw). BD 1 as a chemosensor thus
combines the sensitivity of fluorescence with the convenience
and the aesthetic appeal of a colorimetric assay.
1
H NMR spectra of BD 1 on addition of various
concentrations of Al3+ in CD3CN were recorded to determine
the mode of complexation. Significant spectral changes
observed upon addition of Al3+ to BD 1 are depicted in
Fig. 5. The main peaks considered for assigning the binding
mode of BD 1 : Al3+ are methyl protons (Ha) of dansyl
moiety, triazole ring (Hb) and the ortho position of the
bipyridyl ring (Hc). Methyl protons undergo an overall large
downfield shift of 0.61 ppm upon addition of 1.0 eqv. of Al3+

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c The Royal Society of Chemistry 2010

Published on 18 May 2010 on http://pubs.rsc.org | doi:10.1039/C0CC00119H
Fig. 4 UV-Vis absorption spectra of BD 1 (2.5 mM) in CH3CN upon
adding various concentrations of Al(ClO4)3 (0, 1.25, 2.5, 5, 12.5, 25,
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62.5, 125, 187.5, 250, 500, 750 and 1000 mM). Inset: absorption
intensity in the range 400–600 nm as a function of [Al3+].
salt. This is a clear indication of the direct involvement of
N(CH3)2 in coordinating with Al3+. Similarly, peaks
corresponding to a triazole ring (Hb) and the ortho-proton
of the bipyridyl ring (Hc) were downfield shifted by 0.44 and
0.27 ppm, respectively. Downfield shift of other aromatic
protons from bipyridyl and dansyl rings were also observed.
There was no appreciable change observed in the peak
positions on addition of 41.0 eqv. of Al3+ to BD 1. These
observed downfield shifts of various protons suggest 1 : 1
binding stoichiometry for BD 1 : Al3+ and tetra-coordination
of Al3+ to BD 1 through four nitrogens, two from bipyridyl,
one from triazole ring and another one being the N(CH3)2 of
dansyl moiety. The hexa-coordination of Al3+ can be satisfied
by two solvent molecules (or H2O) or counter ions.
Fig. 5 Binding mode of BD 1Al3+ and 1H NMR spectra of BD 1
with Al(ClO4)3 in CD3CN. (I) BD 1, (II) BD 1 with 0.5 eqv. of Al3+,
(III) BD 1 with 1.0 eqv. of Al3+and (IV) BD 1 with 1.5 eqv. of Al3+.
This journal is 
c The Royal Society of Chemistry 2010
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The 1 : 1 binding stoichiometry determined from 1H NMR,
absorption and emission spectral studies, was also confirmed
by CHNS elemental analysis. Elemental analysis data matched
with the 1 : 1 complex of BD 1 : Al3+ and two molecules of
coordinated water (ESIw). The 1 : 1 binding stoichiometry and
overall hexa-coordination was further confirmed by mass data
of BD 1 : Al3+ complex. MALDI-MS showed exclusively the
formation of the BD 1Al3+2H2O complex [MW: 602.27;
calcd, 602.21 for C29H33AlN7O4S] (ESIw). Coordination of
two water molecules in the BD 1 : Al3+ was also confirmed by
thermogravimetric analysis (ESIw).
In conclusion, synthesis of a new pyrrolidine constrained
bipyridyl-dansyl (BD) chemosensor was achieved through
very simple and high yielding click chemistry. Triazole moiety
formed during click reaction served as both spacer and cation
binding site. Dansyl moiety also plays a dual role as a
reporting unit and cation binding site. Fluoroionophore BD
1 can detect the Al3+ ion on the basis of ICT with high
sensitivity and selectivity. This study opens up the new possibility
of a family of highly selective chemosensors for a range of
cations based on bipyridyl-fluorophore click conjugates.
We thank Prof. C. N. R. Rao, FRS for constant support
and encouragement, JNCASR for providing financial support,
DST, India for a research grant and CSIR, New Delhi, India
for awarding JRF to DM.
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