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that the original red-shifted and weaker emission of the
chemosensor 3–Zn(II) complex was restored. Benesi-
Hildebrand analysis of the binding data revealed strong
association constants; 4.1 · 104 MÀ1 for phosphate ions,
and almost identical values for acetate and fluoride
(4.6 · 104 and 4.2 · 104 MÀ1, respectively). These results
are in agreement with a previous report.4c An attempt
was made to investigate sensing ability in aqueous solu-
tion, however, even small amounts of water resulted in
quenching of the emission, most likely due to the forma-
tion of dye aggregates (see Fig. 3).
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Thus, we have reported an excitation ratiometric fluo-
rescent chemosensor, which signals anion concentra-
tions at the red end of the visible spectrum. The
changes in both the absorbance and the emission spectra
of the Zn(II)–3 complex in the presence of phosphate
anions are especially promising. In addition, this ap-
proach can easily be extended to aqueous media with
appropriate structural modifications. Work towards
these ends is in progress.
Acknowledgments
This work was supported by the Turkish Scientific and
Technological Research Council (TUBITAK) and
Turkish Academy of Sciences (TUBA). A.C. thanks
TUBITAK for a scholarship.
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U.S. Patent 4,774,339, 1988; CAN 112: 160477.
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References and notes
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9. Analytical data for compound 3: 1H NMR (CDCl3,
400 MHz, 298 K) d; 8.45 (d, 2H, J = 4.5 Hz), 7.61–7.06
(m, 15H), 6.51 (d, 2H, J = 8.5 Hz), 3.84 (s, 4H), 3.45 (t, 2H,
J = 6.8 Hz), 2.83 (s, 3H), 2.73 (t, 2H, J = 6.8 Hz), 2.55–2.45
(m, 5H), 2.26 (q, 2H, J = 7.5 Hz), 1.23 (s, 3H), 1.21 (s, 3H),
1.07 (t, 3H, J = 7.5 Hz), 0.92 (t, 3H, J = 7.5 Hz). 13C NMR
(CDCl3, 100 MHz, 298 K) 156.2, 153.2, 148.7, 137.7, 137.4,
136.6, 136.2, 135.2, 134.7, 132.1, 131.8, 131.0, 130.5, 128.0,
127.9, 127.6, 125.3, 124.1, 120.9, 115.6, 114.9, 111.7, 65.2,
57.6, 50.4, 30.4, 17.4, 16.3, 13.6, 13.0, 11.6, 10.6, 10.3. MS
(EI) m/e 722.4 (M+). Elemental analysis: Found: C, 74.63;
H, 6.89; N, 11.39. C45H49BF2N6 requires C, 74.78; H, 6.83;
N, 11.63.
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