Angewandte
Chemie
Morishima, V. Lynch, Angew. Chem. 1991, 103, 1018 – 1020;
mentally relevant alkali and alkaline earth metal ions includ-
ing Li+, Na+, K+, Rb2+, Mg2+, Ca2+, Sr2+, and Ba2+. The
Group 12 Zn2+ and Cd2+ ions, in addition to Cr3+ and Pb2+, did
not inhibit the fluorescence response of 10 to Hg2+. From
Figure 3, it is seen that 10 reveals a high selectivity and
sensitivity for Hg2+ ion. Furthermore, at the concentrations of
the probe employed in our studies, Hg2+ could be detected
down to a concentration of 10À7 m, that is, at concentrations in
the ppb range.[13c,d,e] We also investigated the possible inter-
ference owing to the counteranion(s) used. The results
showed that the selected anions have almost no interaction
with 10 in methanol (see Supporting Information).
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In summary, we have prepared and structurally charac-
terized a new expanded porphyrin, which can be exploited as
a highly sensitive near-infrared-fluorescent chemodosimeter
selective for the detection of Hg2+ ions.
Experimental Section
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A solution of pentafluorobenzaldehyde (1.23 mL, 0.01 mmol) and
pyrrole (715 mL, 0.01 mmol) in dichloromethane (1.0 L) was placed in
a 2.0-L round-bottomed flask under nitrogen. Methanesulfonic acid
(MSA; 450 mL, 7.0 mmol) was added to this solution, and the mixture
was stirred for 30 min. After adding 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ), the solution was stirred for another 30 min
and then passed through a short column of basic alumina. The crude
reaction mixture was separated by column chromatography over
silica gel with CH2Cl2/petroleum ether (2:1 v/v). Three different
colored fractions were obtained, first violet, second red, and last deep
violet, which afforded the regular porphyrin (9–12% yield), the
[26]hexaphyrin(1.1.1.1.1.1) (15–20% yield), and 10 (8–12% yield),
respectively. The violet band was purified by preparative thin-layer
chromatography eluting with CH2Cl2/petroleum ether (7:3 v/v),
followed by protonation with CF3COOH and recrystallization from
a CHCl3/MeOH mixture to give another batch of pure product 10
with satisfactory NMR spectroscopic data. 10: m.p. > 3008C
(decomp); 1H NMR (400 MHz, CD3OD): d = 10.10 (d, J = 4.8 Hz,
1H), 9.75 (d, J = 4.8 Hz, 1H), 9.59–9.48 (m, 5H), 9.42 (d, J = 4.8 Hz,
1H), À3.18 (d, J = 4.8 Hz, 1H), À3.30 (d, J = 4.8 Hz, 1H), À3.82 (d,
J = 4.8 Hz, 1H), À4.26 ppm (d, J = 4.8 Hz, 1H); 19F NMR
(CF3COOH, 376.33 MHz, CD3OD): d = À139.26, À139.54, À140.12,
À149.88, À150.39, À151.73, À151.89, À161.83, À162.38,
À162.67 ppm; HR-MS (ESI): m/z calcd for [M+H]+: 1283.1862;
found: 1283.1864.
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Received: January 20, 2006
Published online: April 3, 2006
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Keywords: fluorescence · mercury · nitrogen heterocycles ·
porphyrinoids · sensors
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Angew. Chem. Int. Ed. 2006, 45, 3150 –3154ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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