Inorganic Chemistry
Article
−
6
Preparation of Metal Ion and Anion Solutions. Stock
final concentration of 1, H O , and metal ion was 5.0 × 10 M,
2
2
+
+
+
−4
−4
solutions (0.1 M) of zirconium(IV) chloride and Li , Na , K ,
5.0 × 10 M, and 1.0 × 10 M, respectively.
2
+
2+
2+
3+
2+
2+
2+
2+
+
2+
2+
Mg , Ca , Ba , Fe , Co , Ni , Cu , Zn , Ag , Cd , Hg ,
(c). With Reducing Agent SnCl . Stock solution of stannous
chloride (0.1 M) was prepared in deionized water. Test
solutions were prepared by placing 30 μL of stock solution of 1,
6.0 μL of Sn solution, 9.0 μL of H O solution, and 3.0 μL of
2
2+
Pb ions in perchlorate salts were prepared in deionized water.
−
−
−
−
−
2−
Stock solutions (0.1 M) of F , Cl , Br , I , H PO , SO ,
2
4
4
−
−
−
−
2+
NO , OAc , HCO , and ClO ions in sodium salts were
3
3
4
2
2
prepared in deionized water.
metal ion solution successively in a vial. The resulting solutions
were diluted to 3.0 mL with ethanol and deionized water to
make a final composition of 99:1, v/v. The final concentration
Synthesis of 2. To a suspension of 1-pyrenecarboxylic acid
0.10 g, 0.41 mmol) in CH Cl (10 mL) was added oxalyl
(
2
2
2+
−6
−3
chloride (0.11 mL, 1.2 mmol). One drop of N,N-
dimethylformamide was injected as a catalyst. The resulting
mixture was stirred at room temperature for 4 h. Evaporation
of the volatiles yielded pyrene-1-carbonyl chloride which was
used without purification for next reaction. To a dispersion
of 1, H O , Sn , and metal ion was 5.0 × 10 M, 1.5 × 10 M,
2 2
4
−
−4
2.0 × 10 M, and 1.0 × 10 M, respectively.
Detection Limit. Detection limit was estimated by plotting
the changes in fluorescence intensities of 1 at 382 nm as a
4+
22
function of log [Zr ] following the reported procedure.
A
of ethylamine hydrochloride (0.17 g, 2.0 mmol) in CH Cl2
linear regression curve was fitted to the intermediate values of
the sigmoidal plot. The point at which this line crossed the
ordinate axis was taken as the detection limit.
2
(10 mL) was added triethylamine (1.4 mL, 10 mmol) and
stirred at room temperature for 10 min. To the resulting
solution, pyrene-1-carbonyl chloride dissolved in CH Cl2
Competition Experiment. Test solutions were prepared
2
(2 mL) was added dropwise. After 2 h of stirring, the reaction
by placing 30 μL of stock solution of 1, 3.0 μL of H O
2
2
mixture was washed with water and evaporated to dryness
followed by crystallization from CH Cl and CH OH to obtain
solution, 3.0 μL of metal ion or anion solution, and 3.0 μL of
4+
2
2
3
Zr solution consecutively in a vial. The resulting solutions
were diluted to 3.0 mL with ethanol and deionized water to
make a final composition of 99:1, v/v. The final concentration
1
2
(90 mg, 81%) as a light yellowish product. H NMR (CDCl ,
3
3
00 MHz): δ 8.56 (d, J = 9.3 Hz, 1H), 8.23−8.01 (m, 8H), 6.15
n+
n−
4+
−6
−4
(
br m, 1H), 3.67 (qd, J = 7.3 and 5.6 Hz, 2H), 1.36 (t, J = 7.3
of 1, H O , M or A , and Zr was 5.0 × 10 M, 5.0 × 10 M,
2
2
13
−4
−4
Hz, 3H). C NMR (CDCl , 150 MHz): δ 169.9, 132.4, 131.3,
1.0 × 10 M, and 1.0 × 10 M, respectively.
3
1
1
1
31.1, 130.7, 128.6, 128.5, 128.5, 127.1, 126.3, 125.7, 125.7,
H NMR Evidence. To a solution of 1 (49 mg, 0.17 mmol)
24.7, 124.4, 124.4, 124.4, 124.3, 35.2, 15.0. HRMS (DIP) m/z
in ethanol (5 mL) was added H O2 (30%, 0.084 mL,
2
+
calcd for C H NO [M + H] 274.1232; found, 274.1234.
0.84 mmol) and ZrCl (79 mg, 0.34 mmol). The mixture was
19
16
4
Anal. Calcd for C H NO: C, 83.49; H, 5.53; N, 5.12. Found:
stirred at room temperature for 5 min and water (10 mL) was
added to the solution. The solid product was filtered and dried
1
9
15
C, 83.13; H, 5.26; N, 5.09.
Synthesis of 1. To a solution of 2 (71 mg, 0.26 mmol) in
toluene (5 mL) was added Lawesson’s reagent (110 mg,
in vacuum. The product was dissolved in CDCl to obtain the
3
1
4+
H NMR spectrum for (1 + Zr + H O ).
2
2
0.27 mmol) and the solution was refluxed for 24 h. The solvent
was evaporated, and the crude product was purified by flash
RESULTS AND DISCUSSION
■
column chromatography (silica gel, ethyl acetate/hexane = 1:3, v/v)
1
Pyrene-ethylthioamide derivative 1 was prepared by the reac-
tion of N-ethylpyrene-1-carboxamide 2, which was obtained
from the reaction of 1-pyrenecarboxylic acid with ethylamine
yield, 81%), with Lawesson’s reagent in toluene (yield, 73%)
(Scheme 1). Diethylthioamide derivative 3 which we used as
to give yellow solid product 1 (54 mg, 73%). H NMR (CDCl ,
3
3
00 MHz): δ 8.31 (d, J = 9.3 Hz, 1H), 8.24−8.01 (m, 8H), 7.63
(
br m, 1H), 4.05 (qd, J = 7.3 and 5.4 Hz, 2H), 1.47 (t, J = 7.3
13
(
Hz, 3H). C NMR (CDCl , 150 MHz): δ 200.7, 138.7, 131.8,
3
21
1
1
31.3, 130.7, 128.6, 128.3, 127.2, 126.4, 126.3, 125.8, 125.5,
24.7, 124.7, 124.6, 123.7, 41.5, 13.4. HRMS (DIP) m/z calcd
+
for C H NS [M + H] 290.1003; found, 290.0998. Anal.
Scheme 1. Preparation of Pyrene-Ethylthioamide Derivative
1 and the Structure of Diethylthioamide Derivative 3
19
16
Calcd for C H NS: C, 78.86; H, 5.22; N, 4.84. Found: C,
19
15
78.80; H, 4.84; N, 4.82.
Synthesis of 3. Compound 3 was prepared by following a
21
previously reported procedure.
Signaling of Zr4+ Ions. Due to the rather uninformative
UV−vis absorption responses of 1 toward surveyed metal ions,
signaling behavior was assessed by fluorescence measurements.
For all measurements, the excitation wavelength was 340 nm.
−4
(
a). Without H O . Stock solution of 1 (5.0 × 10 M) was
2 2
prepared in ethanol. Test solutions were prepared by placing
0 μL of stock solution of 1 and 3.0 μL of metal ion solution
consecutively in a vial. The resulting solutions were diluted to
.0 mL with ethanol and deionized water to make a final
composition of 99:1, v/v. The final concentration of 1 and
3
3
−
6
−4
metal ion was 5.0 × 10 M and 1.0 × 10 M, respectively.
(
b). With H O . Stock solution of H O (0.5 M) was
2
2
2
2
a probe for the important oxidant Oxone was also tested, but
the signaling behavior toward the surveyed metal ions was
significantly inferior to the ethylthioamide derivative 1.
The fluorescence spectrum of probe 1 showed a very weak
emission around 372−455 nm in an aqueous 99% ethanol
prepared in deionized water. Test solutions were prepared by
placing 30 μL of stock solution of 1, 3.0 μL of H O solution,
2
2
and 3.0 μL of metal ion solution consecutively in a vial. The
resulting solutions were diluted to 3.0 mL with ethanol and
deionized water to make a final composition of 99:1, v/v. The
1
635
dx.doi.org/10.1021/ic2019428 | Inorg. Chem. 2012, 51, 1634−1639