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absorption peak at 388 nm until the addition of more than one
equivalent of fluoride ion. Further addition of tetrabutylammo-
nium fluoride exhibited a bathochromic shift of maximum at
388 nm to 483 nm with a distinct ‘naked eye’ colour change from
light yellow to dark purple.
The above observations clearly indicate that the addition of the
first equivalent of fluoride ion may lead to the sequestering of the
metal ion to form a stable ion pair with fluoride ion in solution
which effectively inhibits the anion binding with the receptor
molecule as reported earlier.14 However, when the sequestering
of metal ion gets completed, further addition of fluoride leads to
the enhancement in intensity of the 483 nm peak plausibly due
to the complexation of fluoride ion as expected. Similar results
were obtained when titration of 4a was performed with fluoride
ion in the presence of one equivalent of Cu2+ ion.
In conclusion, we have synthesized and characterized novel
ditopic calix[4]arene based receptors 4a–d that possess both
hydrazone and bipyridyl functions at the lower rim. The synthe-
sized molecular receptors have been determined to recognize
Co2+ and fluoride ions simultaneously. They exhibit a substantial
bathochromic shift to elicit a distinct ‘naked eye’ colour change
for fluoride ions. However, it was determined that Ag+ and Cu2+
ions interfere in the binding of fluoride ion with 4a.
Acknowledgments
The authors gratefully acknowledge the assistance received
from Sophisticated Analytical Instrument Facility, CDRI, Lucknow
for FAB-MS spectra, DST, DBT, MOEF, MFPI and MRD, Govt. of India
for financial assistance and the Council of Scientific and Industrial
Research, India for a senior research fellowship to R. S and S. N. S.
Supplementary data
Supplementary data (synthetic procedures, characterisation
data) associated with this article can be found, in the online
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